CN114864951B - Composite current collector for lithium ion battery cathode and preparation method thereof - Google Patents
Composite current collector for lithium ion battery cathode and preparation method thereof Download PDFInfo
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- CN114864951B CN114864951B CN202210211783.2A CN202210211783A CN114864951B CN 114864951 B CN114864951 B CN 114864951B CN 202210211783 A CN202210211783 A CN 202210211783A CN 114864951 B CN114864951 B CN 114864951B
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 164
- 239000002184 metal Substances 0.000 claims abstract description 164
- 230000007704 transition Effects 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 37
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 32
- 239000010439 graphite Substances 0.000 claims abstract description 30
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011651 chromium Substances 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 3
- 229910000599 Cr alloy Inorganic materials 0.000 claims abstract description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 3
- 239000006230 acetylene black Substances 0.000 claims abstract description 3
- 239000004917 carbon fiber Substances 0.000 claims abstract description 3
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 3
- 239000000788 chromium alloy Substances 0.000 claims abstract description 3
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 229910001000 nickel titanium Inorganic materials 0.000 claims abstract description 3
- 239000010955 niobium Substances 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims description 84
- 238000000151 deposition Methods 0.000 claims description 72
- 230000008021 deposition Effects 0.000 claims description 54
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 32
- 238000000992 sputter etching Methods 0.000 claims description 27
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 23
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 15
- 229920001721 polyimide Polymers 0.000 claims description 15
- 239000004642 Polyimide Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229920001230 polyarylate Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920002312 polyamide-imide Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims 2
- 239000004962 Polyamide-imide Substances 0.000 claims 1
- 239000004695 Polyether sulfone Substances 0.000 claims 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 13
- 239000013543 active substance Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 description 94
- 239000011248 coating agent Substances 0.000 description 71
- 239000000523 sample Substances 0.000 description 25
- 230000001965 increasing effect Effects 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 230000003746 surface roughness Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 210000002381 plasma Anatomy 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
- C23C14/0605—Carbon
-
- 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
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- 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
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon 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
- C23C14/24—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
- C23C14/22—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
-
- 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
-
- 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
- H01M4/661—Metal or alloys, e.g. alloy coatings
- H01M4/662—Alloys
-
- 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
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- 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
Abstract
The invention provides a composite current collector for a lithium ion battery cathode and a preparation method thereof, comprising the following steps: a substrate layer positioned at the center, wherein a first metal layer, a second metal layer, a transition layer and a non-metal layer are respectively and sequentially laminated and deposited from the upper surface to the lower surface of the substrate layer outwards; the first metal layer is made of chromium, nickel or titanium or one of chromium alloy, nickel alloy and titanium alloy; the second metal layer is made of one of copper, aluminum, nickel, titanium, niobium or iron; the nonmetallic layer is made of one of lamellar graphite, carbon nano tubes, acetylene black, graphene and carbon fibers; the material of the transition layer is a mixture of a second metal layer material and a nonmetallic layer material. The composite current collector has stable material performance and good corrosion resistance, and does not react with electrolyte, active substances and the like; the cost is low, the raw materials used are easy to obtain, and the preparation method is suitable for mass production.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite current collector for a lithium ion battery cathode and a preparation method thereof.
Background
The lithium ion battery has the characteristics of high energy density, long cycle life, no memory effect, environmental friendliness and the like, and is widely applied to a plurality of fields such as electronic communication, traffic, energy storage and the like. In lithium ion batteries, the current collector is an extremely important component, and is used as a supporting structure of anode and cathode materials, so that the active material is carried, electrons generated by electrochemical reaction are collected and led to an external circuit, and the process of converting chemical energy into electric energy is realized. Thus, the current collector performance has a non-negligible impact on the overall lithium ion battery performance.
In lithium ion batteries, most of traditional negative current collectors are electrolytic copper foil, and have the problems of high thickness, large mass, poor binding force with active substances, low strength and flexibility, unstable safety and the like, so that the charge and discharge cycle, rate performance and the like of the lithium ion batteries are seriously influenced, the lithium ion batteries have potential safety hazards, and the application of the lithium ion batteries is limited.
Compared with metal materials, the polymer materials have lower density and better mechanical properties, so the current collector using the polymer materials can effectively improve the performance of the lithium ion battery. Patent document CN112151806a discloses an ultra-light multilayer composite current collector and a preparation method thereof, and although the process is simple, the cost is low, and the binding force is good, the corrosion resistance of the composite current collector metal layer and the carbon coating is insufficient. Patent document CN211957791U discloses a negative current collector of a composite structure, which adopts a porous structure to increase the contact area of the surface of a coating and improve the current density and the rate capability of a battery, but the binding force and the corrosion resistance between each layer of the composite structure are insufficient.
Disclosure of Invention
The invention provides a composite current collector with high corrosion resistance and high interface bonding strength for a lithium ion battery cathode and a preparation method thereof, which are used for solving the problems of poor bonding force and insufficient corrosion resistance among layers of a composite structure in the prior art.
The invention relates to a composite current collector for a lithium ion battery cathode, which is characterized by comprising the following components: a substrate layer positioned at the center, wherein a first metal layer, a second metal layer, a transition layer and a non-metal layer are respectively and sequentially laminated and deposited from the upper surface to the lower surface of the substrate layer outwards; the first metal layer is made of metal chromium, nickel or titanium, or one of chromium alloy, nickel alloy and titanium alloy, preferably metal chromium; the second metal layer is made of one of copper, aluminum, nickel, titanium, niobium or iron, preferably copper; the nonmetallic layer is made of one of lamellar graphite, carbon nano tubes, acetylene black, graphene and carbon fibers; the material of the transition layer is a mixture of the second metal layer material and the nonmetallic layer material.
The substrate layer mainly plays a supporting role in the composite current collector, and the mass density is required to be relatively low compared with that of metal (such as copper or aluminum, etc.), so that the overall mass of the composite current collector is small, the weight energy of a lithium ion battery is effectively reduced, and the substrate layer is not corroded in the electrolyte of the lithium ion battery for a long time; the material of the base material layer is at least one selected from polyethylene terephthalate (PET), polyimide (PI), polyethylene naphthalate (PEN), polycarbonate (PC), polyether ether ketone (PEEK), cyclic polyolefin (COC), polyarylate (PAR), polyether sulfone (PES), polyether imide (PEI), polyamide imide (PAI) and flexible conductive glass.
Further, the thickness of the substrate layer is 1 to 15mm, preferably 5 to 10mm; the thickness of the first metal layer is 2-100 nm, preferably 20-40 nm; the thickness of the second metal layer is 100-2000 nm, preferably 200-600 nm; the thickness of the transition layer is 2-100 nm, preferably 10-30 nm; the thickness of the nonmetallic layer is 2 to 100nm, preferably 20 to 60nm.
The first metal layer is used for improving the binding force between the main conductive layer of the composite current collector and the base material in the composite current collector; the composite current collector has higher compactness, can not be corroded in the electrolyte of the lithium ion battery for a long time, has the binding force between the composite current collector and the substrate and the second metal layer reaching 0 level (ISO level), can effectively solve the problem of poor combination between the subsequent metal layer and the substrate layer, and improves the stability of the composite current collector.
The second metal layer is a main carrier for electron transmission, is used as a main conductive layer in the composite current collector, and is used for collecting electrons generated by electrochemistry in the battery and guiding the electrons to an external circuit so as to realize the process of converting chemical energy in the lithium ion battery into electric energy; the composite material has higher compactness and can not be corroded in lithium ion battery electrolyte for a long time.
The transition layer has higher compactness, can not be corroded in the electrolyte of the lithium ion battery for a long time, has the bonding force between the transition layer and the second metal layer and between the transition layer and the nonmetal layer reaching 0 level (ISO level) respectively, and is used for improving the bonding force between the main conductive layer and the nonmetal layer of the composite current collector, improving the stability of the composite current collector and further optimizing the conductive performance of the composite current collector.
The nonmetal layer is in direct contact with the lithium ion battery cathode material and is used for improving the binding force of the composite current collector and the lithium ion battery cathode material and reducing the contact resistance between the composite current collector and the cathode material; the binding force between the composite material and the negative electrode material of the lithium ion battery reaches 0 level (ISO level), so that corrosion of the current collector can be inhibited, and the cycle life of the battery can be prolonged; the interface contact resistance between the anode active material and the current collector can be obviously reduced, and the multiplying power, circulation and other electrochemical performances of the lithium ion battery are improved; the polarization can be reduced, the thermal effect is reduced, the temperature rise in the charging process is restrained, and the safety of the battery is improved.
The preparation method of the composite current collector for the lithium ion battery cathode comprises the following steps:
s1, cleaning a cleaning substrate by adopting a solvent, and rapidly blowing out residual solvent by using high-purity nitrogen;
s2, respectively performing ion etching cleaning on the upper surface and the lower surface of the base material;
s3, plating first metal layers on the upper surface and the lower surface of the base material respectively;
s4, carrying out ion etching cleaning on the outer surface of the first metal layer;
s5, respectively plating second metal layers on the outer surfaces of the first metal layers;
s6, carrying out ion etching cleaning on the outer surface of the second metal layer;
s7, respectively plating transition layers on the outer surfaces of the second metal layers;
s8, respectively plating nonmetallic layers on the outer surfaces of the transition layers;
and S9, carrying out ion etching cleaning on the outer surface of the nonmetallic layer.
Further, steps S2 to S9 are all performed in a vacuum plating apparatus, wherein the vacuum plating apparatus is a magnetron sputtering apparatus or a vacuum evaporation apparatus.
Further, in the steps S2, S4, S6 and S9, the ion etching cleaning is one of ion source cleaning, radio frequency cleaning or self-bias cleaning; the working gas for cleaning is one of argon, hydrogen or oxygen; the cleaning bias voltage is-100 to-800V, preferably-600 to-700V; the cleaning current is 0.2-1.2A, preferably 0.36-0.4A; the cleaning temperature is 30-240 ℃, preferably 50-80 ℃; the cleaning time is 2 to 60 minutes, preferably 15 to 20 minutes.
Further, in the steps S3, S5, S7 and S8, the plating method is at least one of magnetron sputtering deposition, chemical vapor deposition, pulsed laser deposition and ion plating; the deposition current is 2-14A, preferably 8-10A; the deposition temperature is 30-240 ℃, preferably 50-80 ℃; the deposition air pressure is 0.05-10 Pa, preferably 0.15-0.18 Pa; the deposition bias is 0 to-650V, preferably 0 to-200V.
Further, the steps S2 to S9 are performed on a single vacuum chamber or a continuous apparatus with multiple chambers. Because the continuous equipment has high coating speed and high particle energy during coating, the substrate layer is easily heated and wrinkled or even penetrated, so that a single vacuum chamber is preferable.
The ion etching treatment is carried out on the metal layer and the substrate layer, the metal layer and the nonmetal layer of the composite current collector through plasmas, so that the interfacial binding force among materials of each layer is increased, the interfacial binding strength is high, and the compatibility with negative electrode active materials of a lithium ion battery and the like is good; the composite current collector has stable material performance and good corrosion resistance, and does not react with electrolyte, active substances and the like; the cost is low, the raw materials used are easy to obtain, and the preparation method is suitable for mass production.
Drawings
Fig. 1 is a schematic structural view of a composite current collector according to an embodiment of the present invention.
Description of the reference numerals: 10-composite current collector, 101-substrate, 101 a-substrate layer upper surface, 101 b-substrate layer lower surface, 102 a-first upper metal layer, 102 b-first lower metal layer, 103 a-second upper metal layer, 103 b-second lower metal layer, 104 a-upper transition layer, 104 b-lower transition layer, 105 a-third upper non-metal layer, 105 b-third lower non-metal layer.
Fig. 2 shows the results of measuring the contact angle of a coating by using a drop projection contact angle measuring instrument for the composite current collector according to four embodiments of the invention.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
Example 1
The invention will be described in further detail with reference to the accompanying drawings. The drawings are simplified schematic representations illustrating the basic structure of the invention only, and therefore show only the structures relevant to the invention. Meanwhile, in the description of the present invention, the terms "first", "second", and the like are used only to distinguish the description, and are not to be construed as indicating or implying relative importance.
Example 1
A composite current collector for a lithium ion battery cathode is prepared in single-chamber vacuum magnetron sputtering coating equipment by adopting the following steps:
(1) Selecting a polyethylene terephthalate film (PET) plate with the thickness of 8mm as a base material 101, cleaning the plate by using alcohol, and rapidly blowing out residual alcohol by using high-purity nitrogen so as to remove dust and greasy dirt on the surface of the PET base material 101;
(2) Vacuumizing the equipment chamber until the background vacuum is lower than 5E-3Pa, and introducing argon gas to maintain the air pressure at 0.07Pa at 50 ℃; placing the PET substrate 101 on a sample holder, and feeding the sample holder into the cavity; applying a bias voltage of-650V to the sample frame to carry out ion etching cleaning, wherein the cleaning current is 0.4A, and the cleaning time is 20min, so that greasy dirt and impurities on the surface of the PET substrate are removed, the surface roughness of the substrate is increased, and the binding force between the substrate layer and the first metal layer is enhanced;
(3) Maintaining the temperature in the equipment chamber unchanged, and introducing argon to maintain the air pressure at 0.18Pa; a vacuum magnetron sputtering coating method is adopted, a first upper metal layer 102a (Cr coating) and a first lower metal layer 102b (Cr coating) are respectively coated on the upper surface and the lower surface of the PET substrate 101, the deposition current is 10A, the deposition time is 25min, and the thicknesses of the first upper metal layer 102a and the first lower metal layer 102b are 20nm;
(4) Maintaining the temperature in the chamber unchanged, and reducing the air pressure in the equipment chamber to 0.07Pa; applying a bias voltage of-650V to the sample frame, performing ion etching cleaning on the outer surfaces of the first metal layers on the upper surface and the lower surface, wherein the cleaning current is 0.4A, the cleaning time is 20min, and the surface roughness of the first upper metal layer 102a and the first lower metal layer 102b is increased so as to enhance the bonding force between the first upper metal layer and the second metal layer;
(5) Maintaining the temperature in the chamber unchanged, and introducing argon gas to maintain the air pressure at 0.18Pa; a vacuum magnetron sputtering coating method is adopted, a second upper metal layer 103a (Cu coating) and a second lower metal layer 103b (Cu coating) are respectively coated on the outer surfaces of the first upper metal layer 102a and the first lower metal layer 102b, the deposition current is 8A, the deposition time is 90min, and the thicknesses of the second upper metal layer 103a and the second lower metal layer 103b are 520nm;
(6) Maintaining the temperature in the chamber unchanged, and reducing the air pressure in the equipment chamber to 0.07Pa; applying a bias voltage of-650V to the sample frame, performing ion etching cleaning on the outer surfaces of the second metal layers on the upper surface and the lower surface, wherein the cleaning current is 0.4A, the cleaning time is 20min, and the surface roughness of the second upper metal layer 103a and the second lower metal layer 103b is increased so as to enhance the bonding force between the second upper metal layer and the transition layer;
(7) Maintaining the temperature in the chamber unchanged, and introducing argon gas to maintain the air pressure at 0.18Pa; coating a transition layer 104a (simultaneously depositing Cu and a graphite mixed coating) and a lower transition layer 104b (simultaneously depositing Cu and a graphite mixed coating) on the outer surfaces of the second upper metal layer 103a and the second lower metal layer 103b respectively by adopting a vacuum magnetron sputtering coating method, wherein the bias voltage is-200V, the deposition current is 10A, the deposition time is 15min, and the thicknesses of the upper transition layer 104a and the lower transition layer 104b are 15nm;
(8) Maintaining the temperature in the chamber unchanged, and reducing the air pressure to 0.15Pa; a vacuum magnetron sputtering coating method is adopted, a third upper non-metal layer 105a (graphite coating) and a third lower non-metal layer 105b (graphite coating) are respectively coated on the outer surfaces of the upper transition layer 104a and the lower transition layer 104b, bias voltage is-200V, deposition current is 10A, deposition time is 30min, and the thicknesses of the third upper non-metal layer 105a and the third lower non-metal layer 105b are 40nm;
(9) Maintaining the temperature in the chamber unchanged, reducing the air pressure to 0.07Pa, applying a bias voltage of-650V to the sample rack, performing ion etching cleaning on the nonmetallic layers on the upper surface and the lower surface, wherein the cleaning current is 0.4A, the cleaning time is 20min, and the binding force between the nonmetallic layers and negative electrode active substances of the lithium ion battery is enhanced;
and (3) sampling from the equipment to obtain the composite current collector with high corrosion resistance and high interface bonding strength for the lithium ion battery cathode.
Example 2
A composite current collector for a lithium ion battery cathode is prepared in single-chamber vacuum magnetron sputtering coating equipment by adopting the following steps:
(1) Selecting a polyethylene terephthalate film (PET) plate with the thickness of 8mm as a base material 101, cleaning the plate by using alcohol, and rapidly blowing out residual alcohol by using high-purity nitrogen so as to remove dust and greasy dirt on the surface of the PET base material 101;
(2) Vacuumizing the equipment chamber until the background vacuum is lower than 5E-3Pa, and introducing argon gas to maintain the air pressure at 0.07Pa at 50 ℃; placing the PET substrate 101 on a sample holder, and feeding the sample holder into the cavity; applying a bias voltage of-650V to the sample frame to carry out ion etching cleaning, wherein the cleaning current is 0.4A, and the cleaning time is 20min, so that greasy dirt and impurities on the surface of the PET substrate are removed, the surface roughness of the substrate is increased, and the binding force between the substrate layer and the first metal layer is enhanced;
(3) Maintaining the temperature in the equipment chamber unchanged, and introducing argon to maintain the air pressure at 0.18Pa; a vacuum magnetron sputtering coating method is adopted, a first upper metal layer 102a (Ni coating) and a first lower metal layer 102b (Ni coating) are respectively coated on the upper surface and the lower surface of the PET substrate 101, the deposition current is 10A, the deposition time is 25min, and the thicknesses of the first upper metal layer 102a and the first lower metal layer 102b are 20nm;
(4) Maintaining the temperature in the chamber unchanged, and reducing the air pressure in the equipment chamber to 0.07Pa; applying a bias voltage of-650V to the sample frame, performing ion etching cleaning on the outer surfaces of the first metal layers on the upper surface and the lower surface, wherein the cleaning current is 0.4A, the cleaning time is 20min, and the surface roughness of the first upper metal layer 102a and the first lower metal layer 102b is increased so as to enhance the bonding force between the first upper metal layer and the second metal layer;
(5) Maintaining the temperature in the chamber unchanged, and introducing argon gas to maintain the air pressure at 0.18Pa; a vacuum magnetron sputtering coating method is adopted, a second upper metal layer 103a (Cu coating) and a second lower metal layer 103b (Cu coating) are respectively coated on the outer surfaces of the first upper metal layer 102a and the first lower metal layer 102b, the deposition current is 8A, the deposition time is 90min, and the thicknesses of the second upper metal layer 103a and the second lower metal layer 103b are 520nm;
(6) Maintaining the temperature in the chamber unchanged, and reducing the air pressure in the equipment chamber to 0.07Pa; applying a bias voltage of-650V to the sample frame, performing ion etching cleaning on the outer surfaces of the second metal layers on the upper surface and the lower surface, wherein the cleaning current is 0.4A, the cleaning time is 20min, and the surface roughness of the second upper metal layer 103a and the second lower metal layer 103b is increased so as to enhance the bonding force between the second upper metal layer and the transition layer;
(7) Maintaining the temperature in the chamber unchanged, and introducing argon gas to maintain the air pressure at 0.18Pa; coating a transition layer 104a (simultaneously depositing Cu and a graphite mixed coating) and a lower transition layer 104b (simultaneously depositing Cu and a graphite mixed coating) on the outer surfaces of the second upper metal layer 103a and the second lower metal layer 103b respectively by adopting a vacuum magnetron sputtering coating method, wherein the bias voltage is-200V, the deposition current is 10A, the deposition time is 15min, and the thicknesses of the upper transition layer 104a and the lower transition layer 104b are 15nm;
(8) Maintaining the temperature in the chamber unchanged, and reducing the air pressure to 0.15Pa; a vacuum magnetron sputtering coating method is adopted, a third upper non-metal layer 105a (graphite coating) and a third lower non-metal layer 105b (graphite coating) are respectively coated on the outer surfaces of the upper transition layer 104a and the lower transition layer 104b, bias voltage is-200V, deposition current is 10A, deposition time is 30min, and the thicknesses of the third upper non-metal layer 105a and the third lower non-metal layer 105b are 40nm;
(9) Maintaining the temperature in the chamber unchanged, reducing the air pressure to 0.07Pa, applying a bias voltage of-650V to the sample rack, performing ion etching cleaning on the nonmetallic layers on the upper surface and the lower surface, wherein the cleaning current is 0.4A, the cleaning time is 20min, and the binding force between the nonmetallic layers and negative electrode active substances of the lithium ion battery is enhanced;
and (3) sampling from the equipment to obtain the composite current collector with high corrosion resistance and high interface bonding strength for the lithium ion battery cathode.
Example 3
A composite current collector for a lithium ion battery cathode is prepared in single-chamber vacuum magnetron sputtering coating equipment by adopting the following steps:
(1) Selecting a polyimide film (PI) plate with the thickness of 10mm as a base material 101, cleaning by using alcohol, and rapidly blowing out residual alcohol by using high-purity nitrogen so as to remove dust and greasy dirt on the surface of the PI base material 101;
(2) Vacuumizing the equipment chamber until the background vacuum is lower than 5E-3Pa, and introducing argon gas to maintain the air pressure at 0.07Pa at the temperature of 30 ℃; placing the PI substrate 101 on a sample holder, and feeding the sample holder into the chamber; applying a bias voltage of-200V to the sample frame to carry out ion etching cleaning, wherein the cleaning current is 0.2A, and the cleaning time is 10min, so that greasy dirt and impurities on the surface of the PI substrate are removed, the surface roughness of the substrate is increased, and the binding force between the substrate layer and the first metal layer is enhanced;
(3) Maintaining the temperature in the equipment chamber unchanged, and introducing argon to maintain the air pressure at 0.06Pa; a vacuum magnetron sputtering coating method is adopted, a first upper metal layer 102A (Cr coating) and a first lower metal layer 102b (Cr coating) are respectively coated on the upper surface and the lower surface of the PI substrate 101, the deposition current is 2A, the deposition bias voltage is-200V, the deposition time is 60min, and the thicknesses of the first upper metal layer 102A and the first lower metal layer 102b are 10nm;
(4) Maintaining the temperature in the chamber unchanged, and increasing the air pressure in the equipment chamber to 0.07Pa; applying bias voltage of-200V to the sample frame, performing ion etching cleaning on the outer surfaces of the first metal layers on the upper surface and the lower surface, wherein the cleaning current is 0.2A, the cleaning time is 10min, and the surface roughness of the first upper metal layer 102A and the first lower metal layer 102b is increased so as to enhance the bonding force between the first upper metal layer and the second metal layer;
(5) Maintaining the temperature in the chamber unchanged, and introducing argon gas to maintain the air pressure at 0.15Pa; a vacuum magnetron sputtering coating method is adopted, a second upper metal layer 103a (Cu coating) and a second lower metal layer 103b (Cu coating) are respectively coated on the outer surfaces of the first upper metal layer 102a and the first lower metal layer 102b, the deposition current is 10A, the deposition bias voltage is-200V, the deposition time is 180min, and the thicknesses of the second upper metal layer 103a and the second lower metal layer 103b are 1000nm;
(6) Maintaining the temperature in the chamber unchanged, and reducing the air pressure in the equipment chamber to 0.07Pa; applying bias voltage of-200V to the sample frame, performing ion etching cleaning on the outer surfaces of the second metal layers on the upper surface and the lower surface, wherein the cleaning current is 0.2A, the cleaning time is 10min, and the surface roughness of the second upper metal layer 103a and the second lower metal layer 103b is increased so as to enhance the bonding force between the second upper metal layer and the transition layer;
(7) Maintaining the temperature in the chamber unchanged, and introducing argon gas to maintain the air pressure at 0.15Pa; coating a transition layer 104a (simultaneously depositing Cu and a graphite mixed coating) and a lower transition layer 104b (simultaneously depositing Cu and a graphite mixed coating) on the outer surfaces of the second upper metal layer 103a and the second lower metal layer 103b respectively by adopting a vacuum magnetron sputtering coating method, wherein the bias voltage is-200V, the deposition current is 2A, the deposition time is 25min, and the thicknesses of the upper transition layer 104a and the lower transition layer 104b are 5nm;
(8) Maintaining the temperature in the chamber unchanged and the air pressure at 0.15Pa; a vacuum magnetron sputtering coating method is adopted, a third upper non-metal layer 105a (graphite coating) and a third lower non-metal layer 105b (graphite coating) are respectively coated on the outer surfaces of the upper transition layer 104a and the lower transition layer 104b, bias voltage is-200V, deposition current is 10A, deposition time is 80min, and the thicknesses of the third upper non-metal layer 105a and the third lower non-metal layer 105b are 80nm;
(9) Maintaining the temperature in the chamber unchanged, reducing the air pressure to 0.07Pa, applying a bias voltage of-200V to the sample frame, performing ion etching cleaning on the nonmetallic layers on the upper surface and the lower surface, cleaning current is 0.2A, cleaning time is 10min, and enhancing the binding force between the nonmetallic layers and the anode active material of the lithium ion battery;
sampling from the equipment to obtain the composite current collector for the lithium ion battery cathode with high corrosion resistance; however, the first metal layer and the transition layer of example 3 were thin, and the resulting composite current collector had poor bonding strength.
Example 4
A composite current collector for a lithium ion battery cathode is prepared in single-chamber vacuum magnetron sputtering coating equipment by adopting the following steps:
(1) Selecting a polyimide film (PI) plate as a base material 101, cleaning by using acetone, and rapidly blowing out residual acetone by using high-purity nitrogen, so as to remove dust and greasy dirt on the surface of the PI base material 101;
(2) Vacuumizing the equipment chamber until the background vacuum is lower than 5E-3Pa, the temperature is 80 ℃, and introducing argon gas to maintain the air pressure at 0.07Pa; placing the PI substrate 101 on a sample holder, and feeding the sample holder into the chamber; applying bias voltage of-700V to the sample frame to carry out ion etching cleaning, wherein the cleaning current is 0.35A, and the cleaning time is 15min, so that greasy dirt and impurities on the surface of the PI substrate are removed, the surface roughness of the substrate is increased, and the binding force between the substrate layer and the first metal layer is enhanced;
(3) Maintaining the temperature in the equipment chamber unchanged, and introducing argon to maintain the air pressure at 0.18Pa; a vacuum magnetron sputtering coating method is adopted, a first upper metal layer 102a (Cr coating) and a first lower metal layer 102b (Cr coating) are respectively coated on the upper surface and the lower surface of the PI substrate 101, the deposition current is 8A, the deposition bias voltage is-400V, the deposition time is 40min, and the thicknesses of the first upper metal layer 102a and the first lower metal layer 102b are 30nm;
(4) Maintaining the temperature in the chamber unchanged, and reducing the air pressure in the equipment chamber to 0.07Pa; applying bias voltage of-700V to the sample frame, performing ion etching cleaning on the outer surfaces of the first metal layers on the upper surface and the lower surface, wherein the cleaning current is 0.35A, the cleaning time is 15min, and the surface roughness of the first upper metal layer 102a and the first lower metal layer 102b is increased so as to enhance the bonding force between the first upper metal layer and the second metal layer;
(5) Maintaining the temperature in the chamber unchanged and the air pressure in the equipment chamber at 0.06Pa; plating a second upper metal layer 103a (Cu coating) and a second lower metal layer 103b (Cu coating) on the outer surfaces of the first upper metal layer 102A and the first lower metal layer 102b respectively by adopting a vacuum magnetron sputtering coating method, depositing a current 2A, depositing a bias voltage of-200V for 50min, wherein the thicknesses of the second upper metal layer 103a and the second lower metal layer 103b are 210nm;
(6) Maintaining the temperature in the chamber unchanged, and reducing the air pressure in the equipment chamber to 0.07Pa; applying bias voltage of-700V to the sample frame, performing ion etching cleaning on the outer surfaces of the second metal layers on the upper surface and the lower surface, wherein the cleaning current is 0.2A, the cleaning time is 15min, and the surface roughness of the second upper metal layer 103a and the second lower metal layer 103b is increased so as to enhance the bonding force between the second upper metal layer and the transition layer;
(7) Maintaining the temperature in the chamber unchanged, introducing more argon gas to maintain the air pressure at 0.18Pa, and preparing a Cu-graphite mixed coating, wherein the deposition bias voltage is-200V, the deposition current is 10A, the deposition time is 20min, and the thickness is 20nm, so as to prepare an upper transition layer 104a (Cu-graphite mixed coating) and a lower transition layer 104b (Cu-graphite mixed coating) in the composite current collector;
(8) Maintaining the temperature in the chamber unchanged, reducing the air pressure to 0.06Pa, preparing a graphite coating, biasing voltage to 400V, depositing current 2A, depositing for 15min, and thickness 20nm to prepare a third upper non-metal layer 105a (graphite coating) and a third lower non-metal layer 105b (graphite coating) in the composite current collector;
(9) Maintaining the temperature in the chamber unchanged, maintaining the air pressure in the equipment chamber to 0.07Pa, applying bias voltage of-700V to the sample rack, performing ion etching cleaning on the nonmetallic layers on the upper surface and the lower surface, cleaning current is 0.2A, cleaning time is 15min, and enhancing the bonding force of the nonmetallic layers and the anode active substances of the lithium ion battery;
and (3) sampling from the equipment to obtain the composite current collector with high corrosion resistance and high interface bonding strength for the lithium ion battery cathode.
Example 5
A composite current collector for a lithium ion battery cathode is prepared in single-chamber vacuum magnetron sputtering coating equipment by adopting the following steps:
(1) Selecting a polyethylene terephthalate film (PET) plate as a base material 101, cleaning by using acetone, and rapidly blowing out residual acetone by using high-purity nitrogen so as to remove dust and greasy dirt on the surface of the PET base material 101;
(2) Maintaining the temperature in the equipment chamber at 30 ℃, and introducing argon to maintain the air pressure at 0.08Pa; a vacuum magnetron sputtering coating method is adopted, a first upper metal layer 102a (Ti coating) and a first lower metal layer 102b (Ti coating) are respectively coated on the upper surface and the lower surface of the PET substrate 101, the deposition current is 14A, the deposition bias voltage is-500V, the deposition time is 32min, and the thicknesses of the first upper metal layer 102a and the first lower metal layer 102b are 38nm;
(3) Maintaining the temperature in the chamber unchanged, and increasing the air pressure in the equipment chamber to 0.24Pa; plating a second upper metal layer 103a (Ni coating) and a second lower metal layer 103b (Ni coating) on the outer surfaces of the first upper metal layer 102a and the first lower metal layer 102b respectively by adopting a vacuum magnetron sputtering coating method, depositing a current 14A, depositing a bias voltage of-500V for 15min, wherein the thicknesses of the second upper metal layer 103a and the second lower metal layer 103b are 200nm;
(4) Maintaining the temperature in the chamber unchanged, and introducing argon gas to maintain the air pressure at 0.24Pa; coating a transition layer 104A (Ni and graphite mixed coating) and a lower transition layer 104b (Ni and graphite mixed coating) on the outer surfaces of the second upper metal layer 103a and the second lower metal layer 103b respectively by adopting a vacuum magnetron sputtering coating method, depositing bias voltage of-500V, depositing current of 14A for 25min, wherein the thicknesses of the upper transition layer 104A and the lower transition layer 104b are 18nm;
(5) Maintaining the temperature in the chamber unchanged and the air pressure at 0.24Pa; a vacuum magnetron sputtering coating method is adopted, a third upper non-metal layer 105a (graphite coating) and a third lower non-metal layer 105b (graphite coating) are respectively coated on the outer surfaces of the upper transition layer 104A and the lower transition layer 104b, the deposition bias voltage is-500V, the deposition current is 14A, the deposition time is 50min, and the thicknesses of the third upper non-metal layer 105a and the third lower non-metal layer 105b are 46nm;
and (3) sampling from the equipment to obtain the composite current collector with high corrosion resistance and high interface bonding strength for the lithium ion battery cathode.
Example 6
A composite current collector for a lithium ion battery cathode is prepared in single-chamber vacuum magnetron sputtering coating equipment by adopting the following steps:
(1) Selecting a polyethylene terephthalate film (PET) plate as a base material 101, cleaning by using acetone, and rapidly blowing out residual acetone by using high-purity nitrogen so as to remove dust and greasy dirt on the surface of the PET base material 101;
(2) Maintaining the temperature in the equipment chamber at 30 ℃, and introducing argon to maintain the air pressure at 0.08Pa; a vacuum magnetron sputtering coating method is adopted, a first upper metal layer 102a (Cr coating) and a first lower metal layer 102b (Cr coating) are respectively coated on the upper surface and the lower surface of the PET substrate 101, the deposition current is 14A, the deposition bias voltage is-500V, the deposition time is 3min, and the thicknesses of the first upper metal layer 102a and the first lower metal layer 102b are 5nm;
(3) Maintaining the temperature in the chamber unchanged, and increasing the air pressure in the equipment chamber to 0.24Pa; plating a second upper metal layer 103a (Cu coating) and a second lower metal layer 103b (Cu coating) on the outer surfaces of the first upper metal layer 102a and the first lower metal layer 102b respectively by adopting a vacuum magnetron sputtering coating method, depositing a current 14A, depositing a bias voltage of-500V for 15min, wherein the thicknesses of the second upper metal layer 103a and the second lower metal layer 103b are 200nm;
(4) Maintaining the temperature in the chamber unchanged, and introducing argon gas to maintain the air pressure at 0.24Pa; coating a transition layer 104A (Cu and graphite mixed coating) and a lower transition layer 104b (Cu and graphite mixed coating) on the outer surfaces of the second upper metal layer 103a and the second lower metal layer 103b respectively by adopting a vacuum magnetron sputtering coating method, depositing bias voltage of-500V, depositing current of 14A for 8min, wherein the thicknesses of the upper transition layer 104A and the lower transition layer 104b are 5nm;
(5) Maintaining the temperature in the chamber unchanged and the air pressure at 0.24Pa; a vacuum magnetron sputtering coating method is adopted, a third upper non-metal layer 105a (graphite coating) and a third lower non-metal layer 105b (graphite coating) are respectively coated on the outer surfaces of the upper transition layer 104A and the lower transition layer 104b, the deposition bias voltage is-500V, the deposition current is 14A, the deposition time is 8min, and the thicknesses of the third upper non-metal layer 105a and the third lower non-metal layer 105b are 10nm;
and (5) sampling from the equipment to obtain the composite current collector for the lithium ion battery cathode with high corrosion resistance. Since example 6 did not perform the steps of ion cleaning and the like and the first metal layer and the transition layer were thin, the bonding force of the composite current collector was poor.
The performance of the composite current collectors for lithium ion battery cathodes prepared in examples 1 to 6 was tested.
(1) The conductivity and the sheet resistance were measured by a four-point probe apparatus according to the GB/T26074-2010 standard, and the measurement results are shown in Table 1.
(2) The binding force performance of the coating is tested by adopting a hundred-grid method: the composite current collector is placed on a hard and flat plane, the cutting edge of the cutting tool is perpendicular to the composite current collector, the cutting tool is uniformly applied with force, and 10 cuts are performed on the coating at a uniform speed. Repeating the above operation, and performing 10 parallel cuts, which intersect with the original cut at 90 degrees, to form a grid pattern. The grids were repeatedly stuck 2 times using a 3M-600 tape, and the test results were classified according to the test result classification table in GB/T9286-2021, and the test results are shown in table 1.
(3) The contact angles of the coatings were tested using a water drop projection contact angle meter in accordance with the specifications of GB/T30693-2014 (measurement of the contact angle of a plastic film with water), as shown in FIGS. 2a, b, c and d, for the composite current collectors of examples 1, 3, 4 and 6, respectively, using a water drop projection contact angle meter.
Table 1 test results of examples 1 to 6
As can be seen from table 1, the composite current collectors prepared by the methods of examples 1 to 6 have better conductivity and smaller contact angle, which indicates that the composite current collectors prepared by the examples have excellent compactness of each layer of material. In the composite current collector prepared in examples 1-2 and 4-5, the interfaces of the materials of each layer are treated by plasma, and the first metal layer and the transition layer effectively increase the binding force between the polymer substrate and the metal coating, between the metal coating and the nonmetal coating, so that the interface binding strength is effectively enhanced. In examples 2 and 4, since the first metal layer and the transition layer of examples 3 and 6 are thin and the interface between the materials of each layer of example 6 is not plasma treated, the interface bonding strength of the composite current collector prepared in examples 3 and 6 is poor.
Claims (4)
1. A composite current collector for a negative electrode of a lithium ion battery, comprising: a substrate layer positioned at the center, wherein a first metal layer, a second metal layer, a transition layer and a non-metal layer are respectively and sequentially laminated and deposited from the upper surface to the lower surface of the substrate layer outwards; the first metal layer is made of chromium, nickel or titanium or one of chromium alloy, nickel alloy and titanium alloy; the second metal layer is made of one of copper, aluminum, nickel, titanium, niobium or iron; the nonmetallic layer is made of one of lamellar graphite, carbon nano tubes, acetylene black, graphene and carbon fibers; the material of the transition layer is a mixture of the second metal layer material and the nonmetallic layer material; the thickness of the substrate layer is 5-10 mm; the thickness of the first metal layer is 20-40 nm; the thickness of the second metal layer is 200-600 nm; the thickness of the transition layer is 15-20 nm; the thickness of the nonmetallic layer is 20-60 nm;
the preparation method of the composite current collector comprises the following steps:
s1, cleaning a base material by adopting a solvent, and rapidly blowing off residual solvent by using high-purity nitrogen;
s2, respectively performing ion etching cleaning on the upper surface and the lower surface of the base material;
s3, plating first metal layers on the upper surface and the lower surface of the base material respectively;
s4, carrying out ion etching cleaning on the outer surface of the first metal layer;
s5, respectively plating second metal layers on the outer surfaces of the first metal layers;
s6, carrying out ion etching cleaning on the outer surface of the second metal layer;
s7, respectively plating transition layers on the outer surfaces of the second metal layers;
s8, respectively plating nonmetallic layers on the outer surfaces of the transition layers;
s9, carrying out ion etching cleaning on the outer surface of the nonmetallic layer;
the preparation method of the composite current collector comprises the steps S2 to S9, wherein the preparation method is carried out in vacuum coating equipment, and the vacuum coating equipment is a magnetron sputtering device;
in the steps S2, S4, S6 and S9, the ion etching cleaning is one of ion source cleaning, radio frequency cleaning or self-bias cleaning; the working gas for cleaning is one of argon, hydrogen or oxygen; the cleaning bias voltage is-100 to-800V; the cleaning current is 0.2-1.2A; the cleaning temperature is 30-80 ℃; the cleaning time is 2-60 min; in the steps S3, S5, S7 and S8, the plating method is magnetron sputtering deposition, and the deposition current is 2-14A; the deposition temperature is 30-80 ℃; the deposition air pressure is 0.05 Pa to 10Pa; the deposition bias voltage is 0 to-650V.
2. The composite current collector for a negative electrode of a lithium ion battery according to claim 1, wherein the first metal layer is made of chromium metal; the second metal layer is made of copper; the nonmetallic layer is made of lamellar graphite.
3. The composite current collector for a negative electrode of a lithium ion battery according to claim 1, wherein the material of the base material layer is at least one of polyethylene terephthalate, polyimide, polyethylene naphthalate, polycarbonate, polyether ether ketone, cyclic polyolefin, polyarylate, polyether sulfone, polyether imide, polyamide imide, and flexible conductive glass.
4. The composite current collector for a negative electrode of a lithium ion battery according to claim 1, wherein the steps S2 to S9 are performed on a single vacuum chamber or a continuous apparatus of a plurality of chambers.
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| CN103545533A (en) * | 2013-10-18 | 2014-01-29 | 中国第一汽车股份有限公司 | Lithium battery with high specific energy and preparation method for current collector of lithium battery |
| CN111312994A (en) * | 2018-12-11 | 2020-06-19 | 深圳先进技术研究院 | Composite negative plate and preparation method and application thereof |
| CN211957791U (en) * | 2020-03-16 | 2020-11-17 | 陈牧 | Negative current collector with composite structure and energy storage device |
| CN112151806A (en) * | 2020-09-15 | 2020-12-29 | 浙江长宇新材料有限公司 | Ultra-light multilayer composite current collector and preparation method thereof |
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| KR20130016851A (en) * | 2011-08-09 | 2013-02-19 | 도레이첨단소재 주식회사 | Flexible cupper clad laminated film being capable of etching and manufacturing method the same |
| CN103545533A (en) * | 2013-10-18 | 2014-01-29 | 中国第一汽车股份有限公司 | Lithium battery with high specific energy and preparation method for current collector of lithium battery |
| CN111312994A (en) * | 2018-12-11 | 2020-06-19 | 深圳先进技术研究院 | Composite negative plate and preparation method and application thereof |
| CN211957791U (en) * | 2020-03-16 | 2020-11-17 | 陈牧 | Negative current collector with composite structure and energy storage device |
| CN112151806A (en) * | 2020-09-15 | 2020-12-29 | 浙江长宇新材料有限公司 | Ultra-light multilayer composite current collector and preparation method thereof |
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