CN116039191A - Copper-plated polypropylene film for lithium battery current collector and preparation method thereof - Google Patents
Copper-plated polypropylene film for lithium battery current collector and preparation method thereof Download PDFInfo
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- CN116039191A CN116039191A CN202211254176.0A CN202211254176A CN116039191A CN 116039191 A CN116039191 A CN 116039191A CN 202211254176 A CN202211254176 A CN 202211254176A CN 116039191 A CN116039191 A CN 116039191A
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- copper
- lithium battery
- polypropylene
- current collector
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- -1 polypropylene Polymers 0.000 title claims abstract description 103
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 94
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 94
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 150000002085 enols Chemical class 0.000 claims abstract description 9
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 claims abstract description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000003851 corona treatment Methods 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 230000008569 process Effects 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 10
- 238000004880 explosion Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical compound CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- 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
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
-
- 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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/308—Heat stability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/10—Batteries
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a copper-plated polypropylene film for a lithium battery current collector and a preparation method thereof. Mixing enol, polypropylene and an initiator, heating to a molten state, reacting to obtain an intermediate I, further adding anhydrous sodium carbonate and 4-nitrophthalonitrile by taking dimethylformamide as a solvent, and heating under an inert atmosphere to react to obtain the modified polypropylene, wherein the prepared copper-plated polypropylene film can effectively prevent excessive combustion of a battery under the condition of good mechanical properties, and effectively reduce ignition caused by thermal runaway of a lithium battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a copper-plated polypropylene film for a lithium battery current collector and a preparation method thereof.
Background
As the market demand for lithium battery performance increases, the energy density and safety performance of lithium batteries have been the technological direction of efforts to improve. In most cases, the energy density of a lithium battery and the safety performance of a lithium battery are a pair of contradictors, and increasing the energy density of a lithium battery often comes at the expense of the safety performance of a battery. The composite copper foil is a novel lithium battery negative electrode current collector material, and has the advantages of low cost, high safety and high energy density compared with the traditional electrolytic copper foil. (1) low cost: the composite copper foil has lower price sensitivity to copper materials, the raw material cost accounts for about 40% -50%, the raw material cost is obviously lower than 78% of that of the traditional electrolytic copper foil, and the unit production cost of the composite copper foil after the production is about 3.1 yuan/m according to the current copper price estimation 2 Left and right, and along with the technical progress of the equipment links, the cost still has a larger reduction space; (2) safer: the composite copper foil has an insulating substrate and light and thin conducting layer structure, and when the battery is in short circuit, the short circuit current can be cut off or reduced in a short time through fusing and providing a larger resistance by the insulating material, so that the thermal runaway of the battery is effectively prevented; (3) high energy density: the density of the high molecular organic material is lower, the weight of the composite current collector can be greatly reduced, and the composite current collector is also improvedWeight energy density of the battery is raised.
The patent application number 201910642542.1 discloses a multilayer structure lithium battery current collector and a preparation method thereof as well as a lithium battery, wherein the multilayer structure lithium battery current collector comprises a high polymer film, a first binding force enhancing layer covered on the upper surface of the high polymer film, a second binding force enhancing layer covered on the lower surface of the high polymer film, a third material layer covered on the surface of the first binding force enhancing layer and a fourth material layer covered on the surface of the second binding force enhancing layer, a fifth material layer covered on the surface of the third material layer and a sixth material layer covered on the surface of the fourth material layer, a seventh material layer covered on the surface of the fifth material layer and an eighth material layer covered on the surface of the sixth material layer, the third material layer and the fourth material layer are material layers with a conductive function, the fifth material layer and the sixth material layer contain at least one polymer base material, and the seventh material layer and the eighth material layer are material layers with a conductive function, so that the energy density of the lithium battery can be improved and the safety performance of the lithium battery can be improved.
The Chinese patent with application number 201611033528.4 discloses a flexible current collector for a lithium battery and a preparation method thereof, wherein the flexible current collector comprises a flexible substrate layer, a metal conductive coating and a conductive oxidation resistant layer which are sequentially and tightly combined; the flexible substrate layer is one of polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polydimethylsiloxane and polyimide, and the thickness of the flexible substrate layer is 1-20 mu m; the metal conductive coating is one of Cu, al, ni, au and Ag, and the thickness of the metal conductive coating is 0.1-5 mu m; the conductive oxidation-resistant layer comprises at least one of conductive graphite, graphene, carbon nanotubes and carbon nanofibers, and the thickness of the conductive oxidation-resistant layer is greater than 0 and less than 1 μm. The obtained flexible current collector has strong mechanical processability, strong thermal stability and oxidation resistance energy, and small overall mass density.
Disclosure of Invention
In order to solve the problems, the invention provides a copper-plated polypropylene film for a lithium battery current collector and a preparation method thereof, wherein enol, polypropylene and an initiator are mixed and heated to a molten state to react to obtain an intermediate I, and further, dimethylformamide is taken as a solvent, anhydrous sodium carbonate and 4-nitrophthalonitrile are added to react under heating in an inert atmosphere to obtain modified polypropylene, and the prepared copper-plated polypropylene film can effectively prevent excessive combustion of a battery under the condition of good mechanical properties and effectively reduce ignition caused by thermal runaway of the lithium battery.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a copper-plated polypropylene film for a lithium battery current collector comprises a supporting layer, a bonding layer covered on the upper surface of the supporting layer and a metal layer covered on the upper surface of the bonding layer;
the supporting layer is polypropylene; the bonding layer is modified polypropylene; the metal layer is a Cu metal layer;
the preparation method of the modified polypropylene comprises the following steps:
s1, mixing enol, polypropylene and an initiator, heating to a molten state to perform graft copolymerization reaction for 2-4h, preferably 3h, and obtaining an intermediate I, wherein the reaction process is as follows:
s2, taking dimethylformamide as a solvent, adding an intermediate I, anhydrous sodium carbonate and 4-nitrophthalonitrile, heating to 180-200 ℃ for reaction for 18-22 hours, preferably 185 ℃ and 20 hours under inert atmosphere, and carrying out reduced pressure reflux after the reaction is finished to obtain modified polypropylene, wherein the reaction process is as follows:
wherein: r is a hydrocarbon group of 1 to 4 carbons, preferably a hydrocarbon group of 2 carbons.
Further, the initiator is any one of benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, tert-butyl hydroperoxide and p-menthane hydroperoxide, and preferably benzoyl peroxide.
Further, the inert atmosphere is nitrogen or argon, preferably nitrogen.
Further, the preparation method of the copper-plated polypropylene film for the lithium battery current collector comprises the following preparation processes: after the surface of the supporting layer is cleaned, corona treatment is carried out on the surface of the supporting layer, and a bonding layer is compounded on the surface of the supporting layer; then plating a metal layer on the surface of the supporting layer by means of magnetron sputtering and electroplating.
Further, the surface of the supporting layer is cleaned by the following steps: firstly, acetone is used for spraying and cleaning for 10-15min, preferably 12min, and then alcohol is used for cleaning for 8-12min, preferably 10min in an ultrasonic water bath.
The invention has the following beneficial effects:
on one hand, phenyl is introduced into the modified polypropylene prepared by the invention, so that the structure of the modified polypropylene has better thermal stability; on the other hand, as the benzene ring is used as a rigid group, the chemical bond of the benzene ring is difficult to rotate in space, so that the synthesized polymer has good stability, the mechanical property of the synthetic film is enhanced, and in the process of preparing the modified polypropylene, when 3-butene-1-ol is selected as enol, the prepared film has the best performance in all aspects. When short circuit occurs locally, the prepared copper-plated polypropylene film can rapidly cut off a failure circuit, effectively prevent excessive combustion of the battery and effectively reduce the fire and explosion risks caused by thermal runaway of the lithium battery. In addition, when a copper metal layer is deposited on the surface of the bonding layer, a coordination effect is formed between nitrile groups and copper elements contained in the modified polypropylene in the measurement and control sputtering process, so that the bonding effect between the bonding layer and the metal layer can be further enhanced, and the bonding force between film layers is ensured.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be made clearly and completely in connection with the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
The polypropylene used in the invention is purchased from northern Europe chemical industry, singapore TPC; the positive electrode material was purchased from NCM523, a company of beijing liter materials technologies, inc; the negative electrode material was purchased from Shenzhen Bei Terui New energy materials Co., ltd.
Example 1
A copper-plated polypropylene film for a lithium battery current collector comprises a supporting layer, a bonding layer covered on the upper surface of the supporting layer and a metal layer covered on the upper surface of the bonding layer.
Wherein the supporting layer is polypropylene; the bonding layer is modified polypropylene; the metal layer is a Cu metal layer;
the preparation method of the modified polypropylene comprises the following steps:
s1, mixing 75 parts by weight of allyl alcohol, 90 parts by weight of polypropylene and 3 parts by weight of azobisisobutyronitrile, heating to a molten state to perform graft copolymerization reaction, and reacting for 2 hours to obtain an intermediate I, wherein the reaction process is as follows:
in the process, an initiator benzoyl peroxide is decomposed to generate free radicals, hydrogen on tertiary carbon of polypropylene is abstracted by the free radicals to generate polypropylene macromolecule free radicals, and then the polypropylene macromolecule free radicals react with allyl alcohol to obtain a graft intermediate I;
s2, taking 80 parts by weight of dimethylformamide as a solvent, adding 75 parts by weight of an intermediate I, 3 parts by weight of anhydrous sodium carbonate and 70 parts by weight of 4-nitrophthalonitrile, heating to 180 ℃ for reaction for 18 hours under a nitrogen atmosphere, and carrying out reduced pressure reflux after the reaction is finished to obtain modified polypropylene, wherein the reaction process comprises the following steps of:
the preparation method of the copper-plated polypropylene film for the lithium battery current collector comprises the following preparation processes: cleaning the surface of the supporting layer: firstly, acetone is used for spray cleaning for 10min, and then alcohol is used for cleaning for 8min in an ultrasonic water bath; after the surface of the supporting layer is cleaned, corona treatment is carried out on the surface of the supporting layer, and a bonding layer is compounded on the surface of the supporting layer by adopting a film compounding technology; then plating a metal layer on the surface of the supporting layer by means of magnetron sputtering and electroplating.
When the metal layer is deposited on the surface of the bonding layer, the bonding layer is made of a high polymer material, the polarity is small, the surface energy is low, and the adhesion between the plating layer and the bonding layer can be influenced.
The thickness of the support layer of the prepared polypropylene film is 3 mu m, the thickness of the bonding layer is 2 mu m, and the thickness of the metal layer is 0.2 mu m.
Example 2
In this example, compared with example 1, in the preparation of the modified polypropylene, the propenol was changed to 3-buten-1-ol and a part of the preparation conditions was changed, and the rest of the preparation was referred to example 1.
The preparation method of the modified polypropylene comprises the following steps:
s1, mixing 85 parts by weight of 3-butene-1-ol, 100 parts by weight of polypropylene and 5 parts by weight of benzoyl peroxide, heating to a molten state to perform graft copolymerization reaction, and reacting for 3 hours to obtain an intermediate I, wherein the reaction process is as follows:
s2, taking 85 parts by weight of dimethylformamide as a solvent, adding 80 parts by weight of an intermediate I, 5 parts by weight of anhydrous sodium carbonate and 82 parts by weight of 4-nitrophthalonitrile, heating to 185 ℃ for reaction for 20 hours under a nitrogen atmosphere, and carrying out reduced pressure reflux after the reaction is finished to obtain modified polypropylene, wherein the reaction process comprises the following steps of:
the cleaning process for the surface of the supporting layer comprises the following steps: firstly, acetone is used for spray cleaning for 12min, and then alcohol is used for cleaning for 10min in an ultrasonic water bath;
the thickness of the support layer of the prepared polypropylene film is 4 mu m, the thickness of the bonding layer is 3 mu m, and the thickness of the metal layer is 2 mu m.
Example 3
In this example, compared with example 1, in the preparation of the modified polypropylene, the propenol was changed to 5-hexen-1-ol and a part of the preparation conditions was changed, and the rest of the preparation was referred to example 1.
The preparation method of the modified polypropylene comprises the following steps:
s1, mixing 90 parts by weight of 5-hexene-1-ol, 110 parts by weight of polypropylene and 8 parts by weight of cumene hydroperoxide, heating to a molten state to perform graft copolymerization reaction, and reacting for 5 hours to obtain an intermediate I, wherein the reaction process is as follows:
s2, taking 100 parts by weight of dimethylformamide as a solvent, adding 85 parts by weight of an intermediate I, 8 parts by weight of anhydrous sodium carbonate and 88 parts by weight of 4-nitrophthalonitrile, heating to 200 ℃ under the nitrogen atmosphere for reaction for 22 hours, and carrying out reduced pressure reflux after the reaction is finished to obtain modified polypropylene, wherein the reaction process comprises the following steps of:
the cleaning process for the surface of the supporting layer comprises the following steps: firstly, acetone is used for spray cleaning for 15min, and then alcohol is used for cleaning for 12min in an ultrasonic water bath;
the thickness of the support layer of the prepared polypropylene film is 5 mu m, the thickness of the bonding layer is 4 mu m, and the thickness of the metal layer is 4 mu m.
Comparative example 1
In comparison with example 2, the bonding layer was replaced with polypropylene, and the rest of the preparation process was referred to in example 2.
A copper-plated polypropylene film for a lithium battery current collector comprises a supporting layer, a bonding layer covered on the upper surface of the supporting layer and a metal layer covered on the upper surface of the supporting layer; wherein the supporting layer is polypropylene; the bonding layer is polypropylene; the metal layer is a Cu metal layer.
Comparative example 2
In comparison to example 2, the tie layer was replaced with intermediate I for modified polypropylene and the rest of the preparation was as described in example 2.
A copper-plated polypropylene film for a lithium battery current collector comprises a supporting layer, a bonding layer covered on the upper surface of the supporting layer and a metal layer covered on the upper surface of the supporting layer; wherein the supporting layer is polypropylene; the bonding layer is an intermediate I; the metal layer is a Cu metal layer.
The preparation method of the intermediate I comprises the following steps:
s1, mixing 85 parts by weight of 3-butene-1-ol, 100 parts by weight of polypropylene and 5 parts by weight of benzoyl peroxide, heating to a molten state to perform graft copolymerization reaction, and reacting for 3 hours to obtain an intermediate I, wherein the reaction process is as follows:
comparative example 3
In comparison to example 2, the support layer was replaced with polyethylene terephthalate and the rest of the preparation process was as described in example 2.
Comparative example 4
In comparison with example 2, the copper-plated polypropylene film was replaced with a copper foil.
Correlation testing
1. Mechanical properties: the copper-plated polypropylene films prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to mechanical property test, and the test results are shown in Table 1.
TABLE 1
As can be seen from the above test results, the mass density of the copper-plated polypropylene films prepared in examples 1 to 3 and comparative examples 1 to 3 was smaller, and the unit mass of the copper-plated polypropylene films prepared in examples 1 to 3 was smaller than that of comparative examples 1 to 3, especially the unit mass of the copper-plated polypropylene film prepared in example 2 was the smallest, as compared with comparative example 4 in which copper foil was directly used. From the tensile strength test data, it can be found that the copper-plated polypropylene films prepared in examples 1 to 3 have a tensile strength greater than that of comparative examples 1 to 3, and from the comparison of the test data in example 2 and comparative example 3, it can be found that the tensile strength is lowered when the support layer raw material is replaced with polyethylene terephthalate, probably because the bonding force between the modified polypropylene of the bonding layer and the polypropylene is higher than that between the modified polypropylene of the bonding layer and the polyethylene terephthalate. From the elongation test data, it can be found that the elongation of the copper-plated polypropylene films prepared in examples 1 to 3 and comparative examples 1 to 3 was higher than that of the copper foil, wherein the elongation of the copper-plated polypropylene film prepared in example 2 was the largest. While the sheet resistance test revealed that the sheet resistance using the copper foil was the smallest, fang Zuxiao of the copper-plated polypropylene films prepared in examples 1 to 3 were as in comparative examples 1 to 3.
2. The prepared copper-plated polypropylene film is used as a negative electrode current collector, a commercial negative electrode material is coated to prepare a negative electrode plate, a traditional positive electrode current collector is coated with a positive electrode material to prepare a positive electrode plate and a diaphragm, and the positive electrode plate and the diaphragm are assembled into a lithium battery, and overcharge, needling and hot box experiments are carried out.
Overfilling experimental conditions: constant current charging is carried out on a 3C battery of the sample battery to 10V, and the experiment is ended after the charging current is close to 0 and is stabilized for 30 min;
needling experimental conditions: the steel pin had a diameter of 3mm and a needling speed of 20mm/s, and the steel pin was passed through the center of the battery and held in the battery for 30 minutes, and the change of the battery was observed.
Hot box experimental conditions: the fully charged sample cell was warmed to 150 ℃ at a rate of 5 ℃/min, held for 30min, and the cell change was observed. The test results are shown in Table 2.
TABLE 2
| Category(s) | Overcharging | Needling process | 150 ℃ hot box |
| Example 1 | Is not burnt and exploded | Is not burnt and exploded | Is not burnt and exploded |
| Example 2 | Is not burnt and exploded | Is not burnt and exploded | Is not burnt and exploded |
| Example 3 | Is not burnt and exploded | Is not burnt and exploded | Is not burnt and exploded |
| Comparative example 1 | Is not burnt and exploded | Burning, non-explosion | Burning, non-explosion |
| Comparative example 2 | Burning, non-explosion | Burning, non-explosion | Is not burnt and exploded |
| Comparative example 3 | Is not burnt and exploded | Is not burnt and exploded | Is not burnt and exploded |
| Comparative example 4 | Combustion and explosion | Combustion and explosion | Combustion and explosion |
The above test results can show that the lithium battery prepared by adopting the current collector prepared in the embodiment 1-3 has superior safety performance compared with the lithium battery prepared in the comparative embodiment 1-4, and the introduction of the polymer current collector effectively solves the needling safety performance of the battery and effectively ensures the safety of the battery such as overcharge, hot box and the like.
Compared with the prior art, in the invention, enol, polypropylene and an initiator are mixed and heated to a molten state, in the process, the initiator is decomposed to generate free radicals, so that hydrogen on tertiary carbon of polypropylene is abstracted by the free radicals to generate polypropylene macromolecule free radicals, and then the polypropylene macromolecule free radicals and the enol undergo a grafting reaction to obtain an intermediate I; further, dimethyl formamide is used as a solvent, anhydrous sodium carbonate and 4-nitrophthalonitrile are added, and the modified polypropylene is obtained through heating reaction under inert atmosphere. On one hand, phenyl is introduced into the polypropylene, so that the structure of the modified polypropylene has better thermal stability; on the other hand, as the benzene ring is used as a rigid group, the chemical bond of the benzene ring is difficult to rotate in space, so that the synthesized polymer has good stability, and the mechanical property of the synthetic film is enhanced; meanwhile, polypropylene reacts with enol under the action of an initiator in the process of synthesizing modified polypropylene, and test results show that when 3-butene-1-ol is selected as the enol, all aspects of the prepared film have optimal performance, because when an alkyl flexible chain segment is introduced into the polypropylene, the melting point can be effectively reduced, when short circuit occurs locally, the heated part can rapidly collapse, an organic supporting layer can rapidly cut off a failure circuit when heat release occurs, excessive combustion of a battery can be prevented, the ignition and explosion risks caused by thermal runaway of a lithium battery can be effectively reduced, when the alkyl flexible chain segment is too short, the melting point cannot be effectively reduced, further, the rapid collapse can not be guaranteed when the local heating occurs, and the intermolecular winding degree is reduced due to relatively large steric hindrance between molecular chains, so that the mechanical performance is relatively low; and when the segment is too long, the mechanical properties thereof are impaired due to the alkyl group as a soft segment.
Polypropylene as a linear polymer, when chain scission occurs at high temperature, the molecular chains directly break to produce small molecular products. The invention modifies polypropylene, and introduces flexible chain segment and benzene ring group on polypropylene side chain, so that the molecular chains are intertwined, and no matter which structure is broken, only part of the polymer is broken, and after the breaking, the polymer is still connected with the main body of the polymer, so that no small molecule is generated in the initial process of thermal cracking.
In addition, nitrile groups are also introduced into the modified polypropylene structure, when a copper metal layer is deposited on the surface of the bonding layer in the preparation process of the copper-plated polypropylene film, magnetron sputtering is carried out on the surface of the bonding layer before deposition, and in the magnetron sputtering process, coordination effect is formed between the nitrile groups and copper elements contained in the modified polypropylene, so that the bonding effect between the bonding layer and the metal layer can be further enhanced, and the bonding force between the film layers is ensured.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The copper-plated polypropylene film for the lithium battery current collector is characterized by comprising a supporting layer, a bonding layer covered on the upper surface of the supporting layer and a metal layer covered on the upper surface of the bonding layer;
the supporting layer is polypropylene; the bonding layer is modified polypropylene; the metal layer is a Cu metal layer;
the structural formula of the modified polypropylene is as follows:
wherein R is a hydrocarbon group of 1 to 4 carbons.
2. The copper-plated polypropylene film for a lithium battery current collector according to claim 1, wherein the preparation method of the modified polypropylene is as follows:
s1, mixing enol, polypropylene and an initiator, heating to a molten state to perform graft copolymerization reaction, and reacting for 2-4h to obtain an intermediate I, wherein the reaction process is as follows:
s2, taking dimethylformamide as a solvent, adding an intermediate I, anhydrous sodium carbonate and 4-nitrophthalonitrile, heating to 180-200 ℃ for reaction for 18-22 hours in an inert atmosphere, and carrying out reduced pressure reflux after the reaction is finished to obtain modified polypropylene, wherein the reaction process is as follows:
wherein: r is a hydrocarbon group of 1 to 4 carbons.
3. The copper-plated polypropylene film for a lithium battery current collector according to claim 1, wherein the thickness of the support layer is 3 to 5 μm; the thickness of the bonding layer is 2-4 mu m; the thickness of the metal layer is 0.2-4 mu m.
4. The copper-plated polypropylene film for a lithium battery current collector according to claim 2, wherein the initiator is any one of benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, t-butyl hydroperoxide, and p-menthane hydroperoxide.
5. The copper-plated polypropylene film for a lithium battery current collector according to claim 2, wherein the inert atmosphere is nitrogen or argon.
6. The method for preparing the copper-plated polypropylene film for the lithium battery current collector according to any one of claims 1 to 5, wherein the preparation process is as follows: after the surface of the supporting layer is cleaned, corona treatment is carried out on the surface of the supporting layer, and a bonding layer is compounded on the surface of the supporting layer; then plating a metal layer on the surface of the supporting layer by means of magnetron sputtering and electroplating.
7. The method for preparing a copper-plated polypropylene film for a lithium battery current collector according to claim 6, wherein the method for cleaning the surface of the support layer is as follows: firstly, acetone is used for spray cleaning for 10-15min, and then alcohol is used for cleaning for 8-12min in an ultrasonic water bath.
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| CN115073631A (en) * | 2022-08-19 | 2022-09-20 | 河南华佳新材料技术有限公司 | Current collector thin film material for lithium battery |
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| CN115073631A (en) * | 2022-08-19 | 2022-09-20 | 河南华佳新材料技术有限公司 | Current collector thin film material for lithium battery |
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