CN107123812B - Positive current collector, and preparation method and application thereof - Google Patents
Positive current collector, and preparation method and application thereof Download PDFInfo
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- CN107123812B CN107123812B CN201710243721.9A CN201710243721A CN107123812B CN 107123812 B CN107123812 B CN 107123812B CN 201710243721 A CN201710243721 A CN 201710243721A CN 107123812 B CN107123812 B CN 107123812B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a positive current collector, a preparation method and application thereof. The preparation method comprises sequentially plating an adhesion enhancing layer, an aluminum metal coating and an anti-oxidation layer by evaporation coating; the application of the positive electrode current collector is mainly applied to lithium ion batteries. The positive current collector can realize the light weight of the battery and improve the energy density, and can ensure that the aluminum plating layer is not easy to fall off and oxidize.
Description
Technical Field
The invention relates to a positive current collector, a preparation method and application thereof.
Background
The current collector of the anode of the traditional lithium ion battery is aluminum foil. With the development of lithium battery technology, high energy density, light weight and flexibility of lithium ion batteries are pursued by people. And the aluminum foil is thinned, so that the light weight of the lithium ion battery can be realized, and the energy density is improved. However, due to the limitation of the preparation technology, the thickness of the aluminum foil is difficult to reduce (the current aluminum foil can be produced to 8 μm in mass); further, as the aluminum foil becomes thinner, the mechanical strength is lowered, and the workability is lowered, so that a new "thinning technique" is required.
In the prior art, aluminum is plated on plastic (such as PET) as a current collector to improve the energy density of the battery, reduce the cost and lighten the weight of the battery. But the maximum thickness of aluminizing is 2.0 μm (a certain thickness is needed to achieve satisfactory conductivity), which is much thicker than that of aluminizing coating of conventional packaging materials, and the thicker the coating, the easier the aluminizing coating is to be peeled off from the plastic.
In addition, the surface of the aluminum foil needs to be subjected to anti-oxidation treatment, because the aluminum foil is directly contacted with the anode material, and the aluminum foil can be corroded by the electrolyte after a long time, so that the service life of the lithium ion battery is shortened. We find that after the plastic is directly plated with aluminum, the aluminum plating layer is easy to fall off by adopting the traditional anti-oxidation method.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a positive electrode current collector that can reduce the weight of a battery, increase the energy density, and reduce the cost, and can prevent an aluminum plating layer from falling off and oxidizing.
Another aspect of the present invention is to provide a method for preparing a positive electrode current collector.
A third aspect of the present invention is to provide a use of the positive electrode collector.
The invention provides a positive current collector which has a multilayer structure and comprises a plastic film, wherein an adhesive force enhancement layer, an aluminum metal coating and an anti-oxidation layer are sequentially plated on the upper surface and the lower surface of the plastic film.
Further, the plastic film is OPP, PI, PET, CPP or PVC.
Further, the thickness of the plastic film is 2-12 μm.
Further, the adhesion enhancing layer is a metal coating or a non-metal coating, and when the adhesion enhancing layer is a metal coating, the metal is Ni; when the coating is a non-metal coating, the non-metal is SiC or Si3N4Or Al2O3。
Further, the thickness of the adhesion enhancement layer is 10-100 nm.
Further, the thickness of the aluminum metal plating layer is 100-2000 nm.
Further, the oxidation prevention layer is a dense metal layer or a non-metal layer, and when the oxidation prevention layer is a metal layer, the metal is Ni; when a non-metal layer, the non-metal is Al2O3、Si3N4Or SiC.
Further, the thickness of the anti-oxidation layer is 10-100 nm.
The invention provides a preparation method of a positive current collector, which comprises the following steps:
s1, firstly, performing corona treatment on the surface of a plastic film to be coated, then placing a wound roll plastic film into a vacuum chamber of a double-sided reciprocating electron beam evaporation coating machine, sealing the vacuum chamber, and gradually vacuumizing until the vacuum degree reaches 3 multiplied by 10-3-6×10-3Pa, adopting an electron gun to accelerate electron bombardment collision to evaporate the raw material Al2O3Adjusting the unwinding speed, the winding speed and the evaporation capacity, and Al2O3Absorbing heat and gasifying to form Al layer on the surface of the moving film2O3A plating layer, i.e., an adhesion enhancing layer;
s2, Al plating obtained in S12O3Placing the film into a vacuum chamber of a double-sided reciprocating evaporation film plating machine, sealing the vacuum chamber, and gradually vacuumizing until the vacuum degree reaches 4 multiplied by 10-2-6×10-2Pa, heating the evaporation mechanism to 1300-1400 ℃, then conveying the aluminum to the evaporation mechanism, adjusting the unwinding speed, the winding speed and the evaporation capacity, continuously melting and evaporating the aluminum in the evaporation mechanism, and forming an aluminum-plated layer, namely an aluminum metal plating layer, on the surface of the moving film;
s3, placing the aluminizer obtained in the step S2 into a vacuum chamber of a film plating machine, sealing the vacuum chamber, and vacuumizing step by step until the vacuum degree reaches 3 multiplied by 10-3-6×10-3Pa, adopting an electron gun to accelerate electron bombardment collision to evaporate the raw material Al2O3Adjusting the unwinding speed, the winding speed and the evaporation capacity, and Al2O3Absorbing heat and gasifying to form Al layer on the surface of the moving film2O3And the coating is an oxidation preventing layer.
The application of the positive electrode current collector provided by the invention is mainly in batteries, especially in lithium ion batteries.
The beneficial effect of the invention is that,
(1) the weight reduction is realized through the plastic film layer, wherein the weight reduction of the aluminized film current collector can be realized by 50%, the thickness is reduced by 30%, and the energy density of the battery is obviously improved;
(2) the plastic film as a substrate has stronger tensile strength, so that windows such as tension, pressure and the like in the preparation process can be larger, and thus, a material preparation section can realize larger compaction density by adopting higher pressure, and the manufacturing capacity of the process is improved;
(3) the adhesion enhancement layer is plated, so that the falling of the aluminum metal coating can be reduced, and the performance loss of the current collector caused by the easy falling of the aluminum metal coating can be effectively prevented;
(4) the anti-oxidation layer obtained by adopting the film coating mode can solve the problem that an aluminum coating on the plastic falls off and simultaneously achieves the aim of preventing oxidation.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic view of a multilayer structure of a positive electrode current collector of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only preferred embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the positive current collector has a multilayer structure, and includes a plastic film 1, wherein an adhesion enhancing layer 2, an aluminum metal plating layer 3 and an oxidation preventing layer 4 are sequentially plated on the upper and lower surfaces of the plastic film 1.
The weight reduction is realized through the plastic film layer, wherein the weight reduction of the aluminized film current collector can be realized by 50%, the thickness is reduced by 30%, and the energy density of the battery is obviously improved. The plastic film is preferably OPP, PI, PET, CPP or PVC. Wherein OPP is oriented polypropylene plastic; PI is polyimide plastic; PET is polyethylene terephthalate plastic, CPP is casting polypropylene plastic, and PVC is polyvinyl chloride plastic. Further preferably PET, PI, CPP; the thickness of the plastic film is preferably 2 to 12 μm, and more preferably 6 to 10 μm. The temperature resistance of the plastic film is 120-300 ℃.
The adhesion enhancement layer is plated, so that the falling of the aluminum metal coating can be reduced, and the performance loss of the current collector caused by the easy falling of the aluminum metal coating can be effectively prevented. The adhesion enhancement layer is preferably a metal coating or a non-metal coating, and when the adhesion enhancement layer is a metal coating, the metal is Ni; when the coating is a non-metal coating, the non-metal is SiC or Si3N4Or Al2O3More preferably, Al2O3。Al2O3The adhesive property with the plastic film layer and the aluminum metal coating is better, so that the aluminum coating is more difficult to fall off. The thickness of the adhesion enhancing layer is preferably 10 to 100nm, more preferably 10 to 50 nm.
The thickness of the aluminum metal plating layer may be 100 to 2000nm, and more preferably 500 to 1000 nm.
The oxidation preventing layer functions or aims to prevent the aluminum metal plating layer from being oxidized. The anti-oxidation layer can be a compact metal layer or a non-metal layer, and when the anti-oxidation layer is a metal layer, the metal is Ni; when a non-metal layer, the non-metal is Al2O3、Si3N4Or SiC, more preferably Al2O3. When the anti-oxidation layer is obtained by adopting a film coating mode, the problem that an aluminum coating on the plastic falls off can be solved, and the aim of preventing oxidation is fulfilled. The thickness of the oxidation preventing layer may be 10 to 100nm, and more preferably 10 to 50 nm.
This is further illustrated by the following specific examples.
Example 1
A preparation method of a positive current collector comprises the following steps:
s1, firstly, performing corona treatment on the surface of a plastic film to be coated, then placing a wound roll plastic film into a vacuum chamber of a double-sided reciprocating electron beam evaporation coating machine, sealing the vacuum chamber, and gradually vacuumizing until the vacuum degree reaches 3 multiplied by 10-3-6×10-3Pa, adopting an electron gun to accelerate electron bombardment collision to evaporate the raw material Al2O3Adjust and place the medicine wellWinding speed, winding speed and evaporation amount, Al2O3Absorbing heat and gasifying to form Al layer on the surface of the moving film2O3A plating layer, i.e., an adhesion enhancing layer;
s2, Al plating obtained in S12O3Placing the film into a vacuum chamber of a double-sided reciprocating evaporation film plating machine, sealing the vacuum chamber, and gradually vacuumizing until the vacuum degree reaches 4 multiplied by 10-2-6×10-2Pa, heating the evaporation mechanism to 1300-1400 ℃, then conveying the aluminum to the evaporation mechanism, adjusting the unreeling speed, the reeling speed and the evaporation amount, continuously melting and evaporating the aluminum in the evaporation mechanism, and forming a layer of aluminum on the surface of the moving film, namely an aluminum metal coating;
s3, placing the aluminizer obtained in the step S2 into a vacuum chamber of a film plating machine, sealing the vacuum chamber, and vacuumizing step by step until the vacuum degree reaches 3 multiplied by 10-3-6×10-3Pa, adopting an electron gun to accelerate electron bombardment collision to evaporate the raw material Al2O3Adjusting the unwinding speed, the winding speed and the evaporation capacity, and Al2O3Absorbing heat and gasifying to form Al layer on the surface of the moving film2O3And the coating is an oxidation preventing layer. The application of the positive electrode current collector provided by the invention is mainly in batteries, especially in lithium ion batteries.
Thereby obtaining a positive electrode current collector having a multi-layered structure.
The most basic function of the positive electrode current collector obtained in example 1 is to collect current and store the positive electrode material as a carrier, that is, collect current generated by the positive electrode material (battery active material) to form a large current to be output to the outside.
The positive electrode current collector obtained in example 1 was tested, and the test results can be concluded as follows:
(1) the weight reduction is realized through the plastic film layer, wherein the weight reduction of the aluminized film current collector can be realized by 50%, the thickness is reduced by 30%, and the energy density of the battery is obviously improved. (ii) a
(2) The plastic film as a substrate has stronger tensile strength, so that windows such as tension, pressure and the like in the preparation process can be larger, and thus, a material preparation section can realize larger compaction density by adopting higher pressure, and the manufacturing capacity of the process is improved;
(3) the adhesion enhancement layer is plated, so that the falling of the aluminum metal coating can be reduced, and the performance loss of the current collector caused by the easy falling of the aluminum metal coating can be effectively prevented;
(4) the anti-oxidation layer obtained by adopting the film coating mode can solve the problem that an aluminum coating on the plastic falls off and simultaneously achieves the aim of preventing oxidation.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (9)
1. The positive current collector is characterized by having a multilayer structure and comprising a plastic film, wherein an adhesion enhancement layer, an aluminum metal coating and an anti-oxidation layer are sequentially plated on the upper surface and the lower surface of the plastic film, the adhesion enhancement layer is a non-metal coating, and the non-metal is Al2O3。
2. The positive electrode current collector according to claim 1, wherein the plastic film is OPP, PI, PET, CPP or PVC.
3. The positive electrode current collector according to claim 1, wherein the plastic film has a thickness of 2 to 12 μm.
4. The positive electrode current collector of claim 1, wherein the adhesion enhancing layer has a thickness of 10 to 100 nm.
5. The positive electrode current collector of claim 1, wherein the aluminum metal plating layer has a thickness of 100-2000 nm.
6. The positive electrode current collector as claimed in claim 1, whereinCharacterized in that the anti-oxidation layer is a compact metal layer or a non-metal layer, and when the anti-oxidation layer is a metal layer, the metal is Ni; when a non-metal layer, the non-metal is Al2O3、Si3N4Or SiC.
7. The positive electrode current collector according to claim 1, wherein the oxidation preventing layer has a thickness of 10 to 100 nm.
8. A method for preparing a positive electrode current collector according to claim 1, comprising the steps of:
s1, firstly, performing corona treatment on the surface of a plastic film to be coated, then placing a wound roll plastic film into a vacuum chamber of a double-sided reciprocating electron beam evaporation coating machine, sealing the vacuum chamber, and gradually vacuumizing until the vacuum degree reaches 3 multiplied by 10-3-6×10- 3Pa, adopting an electron gun to accelerate electron bombardment collision to evaporate the raw material Al2O3Adjusting the unwinding speed, the winding speed and the evaporation capacity, and Al2O3Absorbing heat and gasifying to form Al layer on the surface of the moving film2O3A plating layer, i.e., an adhesion enhancing layer;
s2, Al plating obtained in S12O3Placing the film into a vacuum chamber of a double-sided reciprocating evaporation film plating machine, sealing the vacuum chamber, and gradually vacuumizing until the vacuum degree reaches 4 multiplied by 10-2-6×10-2Pa, heating the evaporation mechanism to 1300-1400 ℃, then conveying the aluminum to the evaporation mechanism, adjusting the unwinding speed, the winding speed and the evaporation capacity, continuously melting and evaporating the aluminum in the evaporation mechanism, and forming an aluminum-plated layer, namely an aluminum metal plating layer, on the surface of the moving film;
s3, placing the aluminizer obtained in the step S2 into a vacuum chamber of a film plating machine, sealing the vacuum chamber, and vacuumizing step by step until the vacuum degree reaches 3 multiplied by 10-3-6×10-3Pa, adopting an electron gun to accelerate electron bombardment collision to evaporate the raw material Al2O3Adjusting the unwinding speed, the winding speed and the evaporation capacity Al2O3Absorbing heat and gasifying to form Al layer on the surface of the moving film2O3And the coating is an oxidation preventing layer.
9. A battery comprising the positive electrode current collector according to any one of claims 1 to 7.
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| CN201710243721.9A CN107123812B (en) | 2017-04-14 | 2017-04-14 | Positive current collector, and preparation method and application thereof |
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| CN1669163A (en) * | 2002-08-29 | 2005-09-14 | 东洋钢钣株式会社 | Composite current collector |
| CN103326029A (en) * | 2013-06-07 | 2013-09-25 | 深圳市海太阳实业有限公司 | Negative electrode sheet, positive electrode sheet, and lithium ion battery |
| CN104321915A (en) * | 2012-04-17 | 2015-01-28 | 株式会社Lg化学 | Method of manufacturing electrode for lithium secondary cell and electrode manufactured by using same |
| CN105762366A (en) * | 2016-05-04 | 2016-07-13 | 江苏深苏电子科技有限公司 | Composite current collector of lithium ion battery and manufacturing method of composite current collector |
| CN205508941U (en) * | 2016-03-25 | 2016-08-24 | 江苏富朗特新能源有限公司 | Positive negative pole of lithium ion battery that has insulating layer is extremely rolled up |
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2017
- 2017-04-14 CN CN201710243721.9A patent/CN107123812B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1669163A (en) * | 2002-08-29 | 2005-09-14 | 东洋钢钣株式会社 | Composite current collector |
| CN104321915A (en) * | 2012-04-17 | 2015-01-28 | 株式会社Lg化学 | Method of manufacturing electrode for lithium secondary cell and electrode manufactured by using same |
| CN103326029A (en) * | 2013-06-07 | 2013-09-25 | 深圳市海太阳实业有限公司 | Negative electrode sheet, positive electrode sheet, and lithium ion battery |
| CN205508941U (en) * | 2016-03-25 | 2016-08-24 | 江苏富朗特新能源有限公司 | Positive negative pole of lithium ion battery that has insulating layer is extremely rolled up |
| CN105762366A (en) * | 2016-05-04 | 2016-07-13 | 江苏深苏电子科技有限公司 | Composite current collector of lithium ion battery and manufacturing method of composite current collector |
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| CN107123812A (en) | 2017-09-01 |
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