CN114784291B - Flexible current collector with composite structure and preparation method thereof - Google Patents
Flexible current collector with composite structure and preparation method thereof Download PDFInfo
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- CN114784291B CN114784291B CN202210603797.9A CN202210603797A CN114784291B CN 114784291 B CN114784291 B CN 114784291B CN 202210603797 A CN202210603797 A CN 202210603797A CN 114784291 B CN114784291 B CN 114784291B
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- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000000576 coating method Methods 0.000 claims abstract description 55
- 239000011248 coating agent Substances 0.000 claims abstract description 54
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- 238000000034 method Methods 0.000 claims abstract description 15
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 8
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- 229920000642 polymer Polymers 0.000 claims description 8
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 7
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- 229910002804 graphite Inorganic materials 0.000 claims description 7
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
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- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 238000007646 gravure printing Methods 0.000 claims description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920005596 polymer binder Polymers 0.000 claims description 4
- 239000002491 polymer binding agent Substances 0.000 claims description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 4
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 54
- 239000007772 electrode material Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000007788 roughening Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000004643 cyanate ester Substances 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011530 conductive current collector Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a flexible current collector with a composite structure and a preparation method thereof, and belongs to the technical field of new energy battery materials. The flexible current collector in the present invention comprises a flexible non-conductive substrate, a conductive metal layer, and a conductive carbon coating. According to the invention, a layer of conductive metal material is sprayed or thermally compounded on the surface of the flexible non-conductive substrate by a dry method, and then a conductive carbon coating scheme with low cost, high efficiency and excellent performance is coated on the surface of the metal film, so that the prepared flexible current collector has the advantages of lower cost, better adhesive force and excellent electrochemical performance, and meanwhile, the safety performance of the battery can be better solved, and the method is suitable for mass production.
Description
Technical Field
The invention relates to the technical field of new energy battery materials, in particular to a flexible current collector with a composite structure and a preparation method thereof.
Background
Current collectors for electrochemical systems including lithium ion batteries, solid state batteries, supercapacitors and lithium sulfur batteries are mainly aluminum foil and copper foil. The main function of the current collector is to provide good electron conduction capability and connect to an external circuit, and the prior art includes using aluminum foil, copper foil or other substrate films with electron conduction capability as the current collector directly in an electrochemical system, and also includes coating modified current collectors used for improving the good contact capability of the current collector and electrode materials attached to the surface of the current collector, improving the electron conduction capability of interfaces and avoiding corrosion of the current collector by certain substances in the electrochemical system.
The current collector is directly subjected to surface modification by adopting a metal current collector or a metal substrate, and the whole current collector is an electronic conductive path, so that the safety problem of the high-energy-density lithium battery when thermal runaway occurs can not be solved. Meanwhile, the current collector product gradually develops towards the directions of light weight, high interface binding force and high safety under the requirements of high energy density, high safety, quick charge and discharge capability and long cycle life of an application end.
Patent application number 201811401509.1 (application date: 2018-11-22) discloses a lithium ion battery current collector and a preparation method thereof, wherein the current collector adopts a flexible non-conductive substrate, and a metal conductive coating is formed on the surface of the substrate by adopting chemical plating or electroplating. The current collector can improve the strength performance of the current collector and the safety performance of the lithium ion battery.
Patent application number 201710243721.9 (application date: 2017-04-14) discloses a positive electrode current collector, a preparation method and application thereof, wherein the current collector adopts a multilayer structure comprising a plastic film, an adhesive force enhancement layer, an aluminum metal plating layer, an anti-oxidation layer and the like, and the upper surface and the lower surface of the plastic film are plated in sequence. The positive current collector not only can realize the light weight of the battery and improve the energy density, but also can ensure that an aluminized layer is not easy to fall off and oxidize.
Patent application number 201810691419.4 discloses a flexible current collector, a preparation method thereof and application in a lithium ion battery, wherein the current collector adopts a polymer film as a substrate, after surface treatment, a metal conductive carbon coating is sputtered on two sides of the polymer film by a target material by a vacuum sputtering method, and then active material coatings are coated on two sides of the metal conductive carbon coating. The bending machine has the advantages of better flexibility and mechanical strength, and crease or brittle fracture is not easy to generate in the bending process; the polymer film as the material of the substrate has lower mass density, can reduce the overall quality of the battery and improve the energy density of the battery, and has the advantages of high temperature resistance, oxidation resistance, low material cost and convenience for mass production.
The conductive layers on the surface of the flexible non-conductive substrate adopted in the above disclosed patent are all formed by plating a metal conductive layer on the surface of the flexible non-conductive current collector, and the metal conductive layer can cause the following problems in the application process:
1) The contact area between the metal conducting layer and the electrode material layer is smaller due to the contact of the electrode material and the rigid metal material, the electrode material layer swells when the electrode material layer is immersed in the electrode material layer in the later period, the contact area between the electrode material layer and the metal conducting layer is smaller, the interface impedance is larger, the overall electronic conduction capacity of the electrode plate is poorer, and the performance exertion and the cycle service life of an electrochemical system under the condition of high-current charge and discharge are influenced;
2) The contact area between the metal conductive layer and the electrode material layer is smaller, so that the adhesive force deviation between the adhesive in the electrode material layer and the rigid metal conductive layer can be caused, the impedance consistency of the electrode sheet is poor, the current density distribution is uneven, and the electrochemical performance and consistency of an electrochemical system product are seriously influenced;
3) The electrode material layer has a certain dimensional change during the operation of the battery, so that the interface connection between the originally weak metal conductive layer and the electrode material layer is enhanced, and the performance of an electrochemical system is rapidly deteriorated;
4) Plating an oxide layer on the surface of the metal coating, wherein if the oxide layer is a metal layer, the oxidation problem still exists; if the non-metallic materials are SiC, si 3N4 or Al 2O3, si 3N4 and Al 2O3 are non-conductive materials, siC is a semiconductor material, the electron conductivity is greatly hindered, and such a recoating method also results in excessive cost.
Therefore, it is an urgent problem in the art to obtain a flexible current collector having low cost, strong adhesion and excellent electrochemical properties.
Disclosure of Invention
The invention aims to provide a flexible current collector with a composite structure and a preparation method thereof, and the flexible current collector prepared by the invention has lower cost, better adhesive force and more excellent electrochemical performance, and meanwhile, the safety performance of a battery can be better solved, and the flexible current collector is suitable for large-scale batch production.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a flexible current collector with a composite structure, which comprises a flexible non-conductive base material, a conductive metal layer and a conductive carbon coating;
The flexible non-conductive substrate comprises one of polyethylene terephthalate, polyphenylene sulfide, polyether ether ketone, polypropylene, polyethylene, polyimide, o-phenylphenol, polyvinyl chloride, polymethyl methacrylate, polyvinylidene fluoride, polyacrylonitrile, polyacrylic acid, polyvinyl alcohol, polyethylenimine, polyamide, polyphenylsulfone, polysulfone, ethylene-vinyl acetate copolymer and polystyrene; the thickness of the flexible non-conductive substrate is 5-40 mu m;
The conductive carbon coating is prepared from the following raw materials in parts by mass: 0.1-40 parts of a high molecular binder, 0.01-40 parts of a conductive polymer, 20-80 parts of conductive powder, 0.01-10 parts of a crosslinking component, 10-80 parts of a solvent and 0.1-10 parts of a leveling agent; the thickness of the conductive carbon coating is 10-5000 nm.
Further, the metal of the conductive metal layer comprises one or more of Al, cu, fe, ni, na, li, au, ag and stainless steel, and the thickness of the metal layer is 1-10 mu m.
Further, the polymer binder comprises sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, polyacrylic acid, polyamide, polyacrylamide, polyethylene glycol, polyacrylonitrile, polypropylene, polyethylene, polyvinyl chloride, polybutylene terephthalate, polyvinylidene fluoride, polyimide, epoxy resin, polyurethane, polyether ether ketone, polymethyl methacrylate, polyurethane, modified acrylic acid, modified polyurethane, modified styrene-butadiene rubber, and derivatives, blocks, or graft copolymers of the above polymers.
Further, the conductive polymer comprises one or more of polythiophene, polypyrrole, polyaniline and derivatives or blocks and graft copolymers of the above polymers;
The conductive powder comprises one or more of carbon black, acetylene black, carbon nanotubes, carbon fibers, graphite, nano graphite, graphene, fullerene and conductive oxide.
Further, the crosslinking component comprises diacetone acrylamide and/or polyacrylic acid-diacetone acrylamide resin-adipoyl hydrazine co-crosslinks;
the solvent comprises one or more of N-methyl pyrrolidone, water, isopropanol and absolute ethyl alcohol;
The leveling agent comprises one or more of isophorone, diacetone alcohol, ethylene glycol butyl ether, acrylic acid, organic silicon and fluorocarbon.
The invention provides a preparation method of a flexible current collector with a composite structure, which comprises the following steps:
1) Attaching conductive metal to the surface of a flexible non-conductive substrate to obtain a metal film layer current collector;
2) Preparing conductive carbon coating slurry, coating the surface of a metal film layer current collector, and drying to obtain a composite structure flexible current collector;
in step 1), the attaching includes spraying or dry thermal compounding;
The spraying is to sequentially perform thermal spraying and hot pressing treatment on the surface of the flexible non-conductive substrate to obtain a metal film layer current collector;
The dry thermal compounding is to roughen the surface of a flexible non-conductive substrate, then coat thermosetting glue on the surface of the pretreated flexible non-conductive substrate by adopting a gravure printing or backlog coating mode, and then compound a metal film with the glued flexible non-conductive substrate by adopting a heating mode to obtain the metal film layer current collector.
Further, the temperature of the thermal spraying is 100-1000 ℃, and the speed of the thermal spraying is 10-80 s/m; the pressure of the hot pressing treatment is 0.4-0.8 MPa, and the temperature of the hot pressing treatment is 50-120 ℃.
Further, the thermosetting glue solution comprises one or more of acrylic acid, epoxy resin, polyester resin, vinyl ester, bismaleimide, thermosetting polyimide, cyanate ester and polybutadiene resin; the heating temperature is 50-120 ℃.
Further, in the step 2), the coating speed is 1-180 m/min, and the drying temperature is 50-200 ℃.
Further, in the step 2), the viscosity of the conductive carbon coating slurry is 10-2000 mPa.s, the solid content of the conductive carbon coating slurry is 2-35%, and the pH value of the conductive carbon coating slurry is 3-12.
The invention has the beneficial effects that: the problems of adhesion force between the nonmetal layer and the metal layer and interface resistance reduction can be effectively solved, and large-scale low-cost continuous industrial production can be realized more easily.
Detailed Description
The invention provides a flexible current collector with a composite structure, which comprises a flexible non-conductive base material, a conductive metal layer and a conductive carbon coating;
The flexible non-conductive substrate comprises one of polyethylene terephthalate, polyphenylene sulfide, polyether ether ketone, polypropylene, polyethylene, polyimide, o-phenylphenol, polyvinyl chloride, polymethyl methacrylate, polyvinylidene fluoride, polyacrylonitrile, polyacrylic acid, polyvinyl alcohol, polyethylenimine, polyamide, polyphenylsulfone, polysulfone, ethylene-vinyl acetate copolymer and polystyrene; the thickness of the flexible non-conductive substrate is 5-40 mu m;
The conductive carbon coating is prepared from the following raw materials in parts by mass: 0.1-40 parts of a high molecular binder, 0.01-40 parts of a conductive polymer, 20-80 parts of conductive powder, 0.01-10 parts of a crosslinking component, 10-80 parts of a solvent and 0.1-10 parts of a leveling agent; the thickness of the conductive carbon coating is 10-5000 nm.
In the present invention, the flexible nonconductive substrate is preferably one of polyethylene terephthalate, polyphenylene sulfide, polyether ether ketone, polypropylene, polyethylene, polyimide, polyvinyl chloride, polyacrylonitrile, polyacrylic acid, polyvinyl alcohol, polyethylenimine, ethylene-vinyl acetate copolymer, and polystyrene.
In the present invention, the thickness of the flexible nonconductive substrate is preferably 10 to 30 μm, more preferably 15 to 20 μm.
In the present invention, the polymer binder is added to the conductive carbon coating in an amount of 0.1 to 40 parts, preferably 0.5 to 30 parts, more preferably 1.0 to 20 parts, and even more preferably 5 to 10 parts. The polymer binder in the present invention comprises sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, polyacrylic acid, polyamide, polyacrylamide, polyethylene glycol, polyacrylonitrile, polypropylene, polyethylene, polyvinyl chloride, polybutylene terephthalate, polyvinylidene fluoride, polyimide, epoxy resin, polyurethane, polyether ether ketone, polymethyl methacrylate, polyurethane, modified acrylic acid, modified polyurethane, modified styrene butadiene rubber, and one or more of derivatives or blocks and graft copolymers of the above polymers, preferably sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, polyacrylonitrile, polypropylene, polyethylene, polyvinyl chloride, modified polyurethane, modified styrene butadiene rubber, and one or more of derivatives or blocks and graft copolymers of the above polymers, more preferably polypropylene, polyethylene, polyvinyl chloride, modified polyurethane, and one or more of derivatives or blocks and graft copolymers of the above polymers.
In the present invention, the conductive polymer is added to the conductive carbon coating in an amount of 0.01 to 40 parts, preferably 0.1 to 30 parts, more preferably 0.5 to 20 parts, and even more preferably 1.0 to 10 parts. In the present invention, the conductive polymer comprises one or more of polythiophene, polypyrrole, polyaniline, and derivatives, blocks, and graft copolymers of the above polymers, preferably polypyrrole and/or polyaniline, and more preferably polyaniline.
In the present invention, the conductive powder is added to the conductive carbon coating in an amount of 20 to 80 parts, preferably 25 to 75 parts, more preferably 35 to 65 parts, and even more preferably 50 parts. In the present invention, the conductive powder contains one or more of carbon black, acetylene black, carbon nanotubes, carbon fibers, graphite, nanographite, graphene, fullerene and conductive oxide, preferably one or more of carbon black, acetylene black, graphite, nanographite and conductive oxide, more preferably one or more of carbon black, acetylene black and graphite.
In the invention, the amount of the crosslinking component added to the conductive carbon coating is 0.01 to 10 parts, preferably 0.1 to 9 parts, more preferably 0.5 to 8 parts, and even more preferably 2 to 6 parts. In the present invention, the crosslinking component comprises diacetone acrylamide and/or polyacrylic acid-diacetone acrylamide resin-adipoyl hydrazide co-crosslinks, preferably diacetone acrylamide.
In the present invention, the amount of the solvent added to the conductive carbon coating layer is 10 to 80 parts, preferably 20 to 70 parts, more preferably 30 to 60 parts, and even more preferably 45 parts. In the present invention, the solvent contains one or more of N-methylpyrrolidone, water, isopropanol, and absolute ethanol, preferably one or more of N-methylpyrrolidone, water, and isopropanol, and more preferably water and/or isopropanol.
In the invention, the addition amount of the leveling agent in the conductive carbon coating is 0.1-10 parts, preferably 2-8 parts, and more preferably 3-6 parts. In the present invention, the leveling agent contains one or more of isophorone, diacetone alcohol, ethylene glycol butyl ether, acrylic acid, silicone and fluorocarbon, preferably one or more of ethylene glycol butyl ether, acrylic acid and fluorocarbon, and more preferably ethylene glycol butyl ether.
In the invention, the thickness of the conductive carbon coating is 10-5000 nm, preferably 20-4000 nm, more preferably 30-3000 nm, and even more preferably 40-2000 nm.
In the present invention, the metal of the conductive metal layer is preferably one or more of Al, cu, ni, li, ag, fe and stainless steel.
In the present invention, the thickness of the metal layer is 1 to 10. Mu.m, preferably 2 to 5. Mu.m, more preferably 2. Mu.m.
The invention provides a preparation method of a flexible current collector with a composite structure, which comprises the following steps:
1) Attaching conductive metal to the surface of a flexible non-conductive substrate to obtain a metal film layer current collector;
2) Preparing conductive carbon coating slurry, coating the surface of a metal film layer current collector, and drying to obtain a composite structure flexible current collector;
in step 1), the attaching includes spraying or dry thermal compounding;
The spraying is to sequentially perform thermal spraying and hot pressing treatment on the surface of the flexible non-conductive substrate to obtain a metal film layer current collector;
The dry thermal compounding is to roughen the surface of a flexible non-conductive substrate, then coat thermosetting glue on the surface of the pretreated flexible non-conductive substrate by adopting a gravure printing or backlog coating mode, and then compound a metal film with the glued flexible non-conductive substrate by adopting a heating mode to obtain the metal film layer current collector.
In the present invention, the thermal spraying includes arc spraying and/or plasma spraying.
In the invention, the temperature of the thermal spraying is 100-1000 ℃, and the speed of the thermal spraying is 10-80 s/m; preferably, the thermal spraying temperature is 200-800 ℃, and the thermal spraying speed is 40-120 s/min.
In the invention, the pressure of the hot pressing treatment is 0.4-0.8 MPa, and the temperature of the hot pressing treatment is 50-120 ℃; preferably, the pressure of the hot pressing treatment is 0.5-0.7 MPa, and the temperature of the hot pressing treatment is 60-90 ℃.
In the invention, the thermosetting glue solution comprises one or more of acrylic acid, epoxy resin, polyester resin, vinyl ester, bismaleimide, thermosetting polyimide, cyanate ester and polybutadiene resin, and preferably one or more of acrylic acid, epoxy resin, polyester resin, vinyl ester and thermosetting polyimide.
In the invention, the heating temperature is 50-120 ℃, preferably 60-100 ℃.
In the present invention, in the step 2), the coating speed is 1 to 180 m/min, preferably 2 to 150 m/min, and more preferably 10 to 140 m/min; the temperature of the drying is 50-200 ℃, preferably 60-150 ℃, and more preferably 100-120 ℃.
In the present invention, in the step 2), the viscosity of the conductive carbon coating paste is 10 to 2000mpa·s, preferably 20 to 190 mpa·s, more preferably 100 to 180mpa·s, still more preferably 200 to 160 mpa·s; the solid content of the conductive carbon coating slurry is 2-35%, preferably 5-30%, more preferably 10-25%, and even more preferably 15%; the pH is 3 to 12, preferably 4 to 10, more preferably 5 to 8.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the flexible current collector with the composite structure comprises the following steps:
1) The flexible non-conductive substrate adopts a PET film with the thickness of 12 mu m, and 60KW corona surface roughening treatment is carried out on the PET film;
2) And heating Al powder particles to a semi-molten state at 300 ℃ by using a direct-current non-transfer plasma arc as a heat source by adopting a plasma spraying method, spraying the Al powder particles onto the surface of the pretreated flexible non-conductive substrate at a high speed of 20s/m to form a conductive metal layer with firm adhesive force, and performing hot pressing treatment at 0.7MPa and 90 ℃ to obtain the metal film layer current collector, wherein the thickness of the conductive metal layer is 2 mu m.
3) 15 Parts of isopropanol, 1.0 part of lithium carboxymethyl cellulose, 5 parts of isophorone and 25 parts of acetylene black are mixed and then added into a premixing and dispersing machine for premixing for 1h, and then 0.05 part of polypyrrole and 2 parts of diacetone acrylamide are added into the dispersing machine for premixing for 2h, so as to obtain premixed conductive carbon coating slurry; and adding the premixed conductive carbon coating slurry into a sand mill, and dispersing for 5 times to obtain the conductive carbon coating slurry.
4) And adding the conductive carbon coating slurry into a feed barrel of a coating machine, pretreating a conductive metal layer through a corona treatment device, coating by adopting a normal phase printing type coating machine, baking and drying by adopting a 90 ℃ oven, wherein the coating speed is 150 m/min, rolling a finished product, and the thickness of the conductive carbon coating is 300nm to prepare the composite structure flexible current collector.
Comparative example
The current collector of the comparative example was identical to the current collector of example 1, except that the current collector of the comparative example was a non-metallic current collector prepared by a vacuum sputtering method, which did not include a conductive carbon coating.
To examine the performance of the above two groups of prepared current collectors, lithium iron phosphate positive electrode slurry was coated on the two current collectors prepared in example 1 and comparative example using a transfer coater, dried, and then pressed into a sheet using a roll press to obtain an electrode sheet.
Detecting physical properties of the prepared electrode plate:
1. And (3) pole piece resistance test: the four-probe tester was used to test the resistance of the rolled electrode sheet with an area of 150 x 200mm prepared in this example 1, the spacing between each test point was 30mm, and 25 data were tested. The resistance of the electrode plate prepared in the embodiment 1 is stable at 35.1 and the difference is less than or equal to 0.1 and the resistance of the electrode plate prepared in the comparative example fluctuates between 112 and 127 and the average value is 121 and the difference reaches 15.
2. Mechanical properties: the peel strength of the electrode sheet was measured by using a 500N tensile tester, the peel strength of the electrode sheet prepared in example 1 was 185.0N/m, and the peel strength of the electrode sheet prepared in comparative example was 36N/m.
Example 2
The preparation method of the flexible current collector with the composite structure comprises the following steps:
1) The flexible non-conductive substrate adopts a PE film with the thickness of 10 mu m, and the PE film is subjected to 20KW corona surface roughening treatment;
2) Adopting an electric arc spraying method, utilizing heat generated by an electric arc to melt Cu metal wires, wherein the melting temperature is 900 ℃, spraying a melted part of the Cu metal wires to the surface of a pretreated flexible non-conductive substrate by compressed air flow at the speed of 30s/m to form a compact conductive metal layer, and then carrying out hot pressing treatment at the temperature of 0.6MPa and 70 ℃ to obtain a metal film layer current collector, wherein the thickness of the conductive metal layer is 3 mu m;
3) Mixing 45 parts of absolute ethyl alcohol, 18 parts of polyacrylonitrile, 2 parts of diacetone alcohol and 50 parts of carbon black, adding into a premixing and dispersing machine for premixing for 2 hours, and adding 0.2 part of polyaniline and 0.5 part of diacetone acrylamide into the dispersing machine for premixing for 2 hours to obtain premixed conductive carbon coating slurry; and adding the premixed conductive carbon coating slurry into a ball mill, and dispersing for 4 times to obtain the conductive carbon coating slurry.
4) And adding the conductive carbon coating slurry into a feed barrel of a coating machine, pretreating a conductive metal layer through a corona treatment device, wherein the corona power is 30KW, then coating by adopting a normal phase printing type coating machine, baking and drying through a baking oven at 100 ℃, wherein the coating speed is 180 meters/min, rolling a finished product, and the thickness of the conductive carbon coating is 200nm to prepare the flexible current collector.
The current collector prepared in example 2 was prepared into an electrode sheet by the same method as in example 1, the resistance of the electrode sheet was tested to 36.5. OMEGA, the difference was 0.1. OMEGA, and the peel strength was 196.3N/m.
Example 3
The preparation method of the flexible current collector with the composite structure comprises the following steps:
1) The flexible non-conductive substrate adopts a CPP film with the thickness of 9 mu m, and the CPP film is firstly subjected to 30KW corona surface roughening treatment;
2) Carrying out roughening pretreatment on the surface of a flexible non-conductive substrate by adopting a dry thermal compounding method, coating thermosetting glue solution on the surface of the pretreated flexible non-conductive substrate by adopting a gravure printing or backlog coating mode, and compounding a 20 mu m conductive metal film with the glued flexible non-conductive substrate at 100 ℃ to obtain a metal film layer current collector;
3) 60 parts of deionized water, 23 parts of polyethylene glycol, 5 parts of ethylene glycol butyl ether and 35 parts of graphite are mixed and then added into a premixing and dispersing machine for premixing for 3 hours, and 10 parts of polythiophene and 0.02 part of diacetone acrylamide are added into the dispersing machine for premixing for 2 hours, so as to obtain premixed conductive carbon coating slurry; and adding the premixed conductive carbon coating slurry into a homogenizer, and dispersing for 5 times to obtain the conductive carbon coating slurry.
4) And adding the conductive carbon coating slurry into a feed barrel of a coating machine, pretreating a conductive metal layer through a corona treatment device, coating by adopting a normal phase printing type coating machine, baking and drying through an oven at 80 ℃ at a coating speed of 120 m/min, rolling a finished product, and preparing the flexible current collector with the conductive carbon coating thickness of 200 nm.
The current collector prepared in example 3 was prepared into an electrode sheet by the same method as in example 1, the resistance of the electrode sheet was measured to be 35.2. OMEGA, the difference was not more than 0.1. OMEGA, and the peel strength was 188.6N/m.
From the above embodiments, the present invention provides a flexible current collector with a composite structure and a method for preparing the same. According to the invention, by improving the compounding mode of the conductive metal layer and the flexible non-conductive substrate and adopting a thermal spraying method and a dry thermal compounding method, the conductive metal is attached to the surface of the flexible non-conductive substrate, so that the interface problem and the adhesion problem between the conductive metal layer and the electrode material layer are effectively solved, the connection between the flexible current collector and the electrode material coated on the surface of the current collector can be better realized, the larger dimensional change of the electrode material layer in the working process can be better adapted, and meanwhile, the effective surface area of the current collector for conducting electrons can be increased, thereby reducing the internal resistance of a battery, reducing the heating value of the battery and further improving the safety performance, and the advantages are beneficial to improving the performance of an electrochemical system using the current collector. Compared with the prior art, the flexible current collector has the advantages of lower cost, better adhesive force and excellent electrochemical performance, and meanwhile, the safety performance of the battery can be better solved, and the flexible current collector is suitable for mass production.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The composite structure flexible current collector is characterized by comprising a flexible non-conductive substrate, a conductive metal layer and a conductive carbon coating;
The flexible non-conductive substrate comprises one of polyethylene terephthalate, polyphenylene sulfide, polyether ether ketone, polypropylene, polyethylene, polyimide, o-phenylphenol, polyvinyl chloride, polymethyl methacrylate, polyvinylidene fluoride, polyacrylonitrile, polyacrylic acid, polyvinyl alcohol, polyethylenimine, polyamide, polyphenylsulfone, polysulfone, ethylene-vinyl acetate copolymer and polystyrene;
the thickness of the flexible non-conductive substrate is 5-40 mu m;
the conductive carbon coating is prepared from the following raw materials in parts by mass: 0.1 to 40 parts of high molecular binder, 0.01 to 40 parts of conductive polymer, 20 to 80 parts of conductive carbon powder, 0.01 to 10 parts of crosslinking component, 10 to 80 parts of solvent and 0.1 to 10 parts of flatting agent;
the thickness of the conductive carbon coating is 10-5000 nm;
The preparation method of the composite structure flexible current collector comprises the following steps:
1) Attaching conductive metal to the surface of a flexible non-conductive substrate to obtain a metal film layer current collector;
2) Preparing conductive carbon coating slurry, coating the surface of a metal film layer current collector, and drying to obtain a composite structure flexible current collector;
In step 1), the attaching includes spraying or dry thermal compounding;
The spraying is to sequentially perform thermal spraying and hot pressing treatment on the surface of the flexible non-conductive substrate to obtain a metal film layer current collector;
The dry thermal compounding is to roughen the surface of a flexible non-conductive substrate, then coat thermosetting glue solution on the surface of the pretreated flexible non-conductive substrate by adopting a gravure printing or backlog coating mode, and then compound a metal film with the glued flexible non-conductive substrate by adopting a heating mode to obtain a metal film layer current collector;
The temperature of the thermal spraying is 100-1000 ℃, and the speed of the thermal spraying is 10-80 s/m;
The pressure of the hot pressing treatment is 0.4-0.8 MPa, and the temperature of the hot pressing treatment is 50-100 ℃;
the thermosetting glue solution comprises one or more of acrylic acid, epoxy resin, polyester resin, vinyl ester, bismaleimide, thermosetting polyimide, cyanate and polybutadiene resin;
the heating temperature is 50-120 ℃;
in the step 2), the coating speed is 1-180 m/min, and the drying temperature is 50-200 ℃.
2. The composite structure flexible current collector of claim 1, wherein the metal of the conductive metal layer comprises one or more of Al, cu, fe, ni, na, li, au, ag and stainless steel, and the thickness of the metal layer is 1-10 μm.
3. The flexible current collector of claim 2, wherein the polymer binder comprises sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, polyacrylic acid, polyamide, polyacrylamide, polyethylene glycol, polyacrylonitrile, polypropylene, polyethylene, polyvinyl chloride, polybutylene terephthalate, polyvinylidene fluoride, polyimide, epoxy resin, polyurethane, polyether ether ketone, polymethyl methacrylate, modified acrylic acid, modified polyurethane, modified styrene-butadiene rubber, and derivatives, blocks, graft copolymers of the above polymers.
4. A composite structure flexible current collector according to any of claims 1-3, wherein the conductive polymer comprises polythiophene, polypyrrole, polyaniline and one or more of derivatives, blocks and graft copolymers of the above polymers;
The conductive carbon powder body comprises one or more of carbon black, carbon nano tubes, carbon fibers, graphite, graphene and fullerene.
5. The composite structure flexible current collector of claim 4, wherein the crosslinking component comprises diacetone acrylamide and/or polyacrylic acid-diacetone acrylamide resin-adipoyl hydrazide co-crosslinks;
the solvent comprises one or more of N-methyl pyrrolidone, water, isopropanol and absolute ethyl alcohol;
The leveling agent comprises one or more of isophorone, diacetone alcohol, ethylene glycol butyl ether, acrylic acid, organic silicon and fluorocarbon.
6. The method for preparing the composite structure flexible current collector as claimed in any one of claims 1 to 5, comprising the steps of:
1) Attaching conductive metal to the surface of a flexible non-conductive substrate to obtain a metal film layer current collector;
2) Preparing conductive carbon coating slurry, coating the surface of a metal film layer current collector, and drying to obtain a composite structure flexible current collector;
In step 1), the attaching includes spraying or dry thermal compounding;
The spraying is to sequentially perform thermal spraying and hot pressing treatment on the surface of the flexible non-conductive substrate to obtain a metal film layer current collector;
The dry thermal compounding is to roughen the surface of a flexible non-conductive substrate, then coat thermosetting glue on the surface of the pretreated flexible non-conductive substrate by adopting a gravure printing or backlog coating mode, and then compound a metal film with the glued flexible non-conductive substrate by adopting a heating mode to obtain the metal film layer current collector.
7. The method according to claim 6, wherein in the step 2), the viscosity of the conductive carbon coating paste is 10 to 2000 mpa.s, the solid content of the conductive carbon coating paste is 2 to 35%, and the pH value is 3 to 12.
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| CN1992398A (en) * | 2005-12-30 | 2007-07-04 | 比亚迪股份有限公司 | Collector, lithium secondary battery comprising the collector and method for preparation the same |
| JP2008207404A (en) * | 2007-02-23 | 2008-09-11 | Mitsubishi Plastics Ind Ltd | Conducting film and composite film having conducting film |
| CN110718674A (en) * | 2019-10-15 | 2020-01-21 | 宁波铵特姆新能源科技有限公司 | Current collector conductive coating and preparation method thereof |
| CN111048787A (en) * | 2019-12-11 | 2020-04-21 | 合肥国轩高科动力能源有限公司 | Manufacturing method of flexible composite current collector |
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| CN1992398A (en) * | 2005-12-30 | 2007-07-04 | 比亚迪股份有限公司 | Collector, lithium secondary battery comprising the collector and method for preparation the same |
| JP2008207404A (en) * | 2007-02-23 | 2008-09-11 | Mitsubishi Plastics Ind Ltd | Conducting film and composite film having conducting film |
| CN110718674A (en) * | 2019-10-15 | 2020-01-21 | 宁波铵特姆新能源科技有限公司 | Current collector conductive coating and preparation method thereof |
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