CN116487601A - Nano metal coating and application thereof, composite current collector base film and composite current collector - Google Patents
Nano metal coating and application thereof, composite current collector base film and composite current collector Download PDFInfo
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- CN116487601A CN116487601A CN202310530036.XA CN202310530036A CN116487601A CN 116487601 A CN116487601 A CN 116487601A CN 202310530036 A CN202310530036 A CN 202310530036A CN 116487601 A CN116487601 A CN 116487601A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 87
- 239000002184 metal Substances 0.000 title claims abstract description 87
- 239000011248 coating agent Substances 0.000 title claims abstract description 76
- 238000000576 coating method Methods 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 229920000098 polyolefin Polymers 0.000 claims abstract description 37
- 239000000853 adhesive Substances 0.000 claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 39
- 229910052802 copper Inorganic materials 0.000 claims description 23
- 239000010949 copper Substances 0.000 claims description 23
- -1 polypropylene Polymers 0.000 claims description 18
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 8
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 239000002923 metal particle Substances 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 24
- 239000002002 slurry Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000012462 polypropylene substrate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000001755 magnetron sputter deposition Methods 0.000 description 7
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 6
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 6
- 238000003618 dip coating Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000006578 abscission Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000007760 metering rod coating Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009736 wetting Methods 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
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- 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 nano metal coating, application, a composite current collector base film and a composite current collector; wherein the nano metal coating comprises the following components in parts by mass: 0.3-1 part of metal nano particles, 0.02-2 parts of adhesive, 0.1-1 part of surfactant and 0.5-5 parts of dispersing agent. The nano metal coating can be uniformly coated on the surface of the polyolefin film, so that a composite current collector base film with the nano metal coating is formed, and the polarity and conductivity of the composite current collector base film can be enhanced by introducing the nano metal coating containing nano metal particles on the polyolefin base material, so that the metal layer can be deposited more uniformly and has better adhesive force when the metal layer is deposited on the composite current collector base film.
Description
Technical Field
The invention relates to the field of battery manufacturing, in particular to a nano metal coating for a current collector base film and application thereof.
Background
Current collectors, which are structures or parts for collecting current, are mainly used for collecting current generated by battery active materials so as to form a larger current output to the outside in secondary batteries, and common current collectors include metal foils, composite current collectors and the like.
Compared with the traditional current collector (aluminum foil or copper foil), the composite current collector can reduce metal consumption, improve energy density and safety, and is expected to be widely applied to secondary batteries. Composite current collectors are typically prepared by depositing a metallic copper or aluminum layer having a thickness of about 1 micron on a polymeric base film (e.g., polyolefin, polyester, polyimide).
However, the polymer base film which is widely used at present is polyolefin, and polyolefin belongs to nonpolar polymer, and the bonding force between the polyolefin and polar metals such as copper, aluminum and the like is poor, so that in the process of a composite current collector, the metals are not easy to deposit on a polyolefin substrate, even if the metals can be deposited, the conditions of uneven thickness of a metal deposition layer and poor adhesive force on the base film easily occur, the product yield is seriously affected, and the application of the polyolefin as a base film in the development of the composite current collector is limited, so that the problem is a technical problem to be solved in the field.
Disclosure of Invention
The invention provides a nano metal coating for a current collector base film and application thereof, and by configuring the nano metal coating capable of being attached to a polyolefin film, the deposition effect of a metal layer on the polyolefin base film can be effectively improved.
According to a first aspect, the application provides a nano metal coating for a current collector base film, wherein the nano metal coating comprises the following components in parts by mass:
0.3-1 part of metal nano particles, 0.02-2 parts of adhesive, 0.1-1 part of surfactant and 0.5-5 parts of dispersing agent.
In an alternative embodiment, the metal nanoparticles are nano silver or nano copper.
In an alternative embodiment, the metal nanoparticles have a particle size of 40-80nm.
In an alternative embodiment, the adhesive is one or more of sodium hydroxymethyl cellulose and polyacrylic acid; and/or
The surfactant is one or more of sodium dodecyl benzene sulfonate, polyhydroxy ammonium polyacrylate and ethylene oxide polymer; and/or
The dispersing agent is one or more of polyvinylpyrrolidone, ethylene glycol and isopropanol.
According to a second aspect, the present application provides the use of a nano-metal coating as described above in a current collector.
According to a third aspect, the present application provides a composite current collector substrate film comprising the above-described nano-metal coating; and
a polyolefin substrate, the nano-metal coating being attached to opposite side surfaces of the polyolefin substrate.
In an alternative embodiment, the polyolefin substrate is at least one of polypropylene and its derivatives, polyethylene and its derivatives, copolymers of polypropylene and its derivatives and polyethylene and its derivatives.
In an alternative embodiment, the polyolefin substrate has a thickness of 3 to 8 μm.
In an alternative embodiment, the nano-metal coating has a thickness of 30-110nm.
According to a fourth aspect, the present application provides a composite current collector comprising the composite current collector base film described above; and
and the metal layer is deposited on at least one side surface of the composite current collector base film.
The beneficial effects of this application lie in: the nano metal coating can be uniformly coated on the surface of the polyolefin film, so that a composite current collector base film with the nano metal coating is formed, and the polarity and conductivity of the composite current collector base film can be enhanced by introducing the nano metal coating containing nano metal particles on the polyolefin base material, so that the metal layer can be deposited more uniformly and has better adhesive force when the metal layer is deposited on the composite current collector base film.
Drawings
FIG. 1 is a diagram of a composite current collector base film stack in one embodiment of the present application;
FIG. 2 is a graph showing the morphology of nano-metal particles in a nano-metal coating according to one embodiment of the present application.
Reference numerals: a nano metal coating 1 and a polyolefin substrate 2.
Detailed Description
The invention will be described in further detail below with reference to the drawings by means of specific embodiments. Wherein like elements in different embodiments are numbered alike in association. In the following embodiments, numerous specific details are set forth in order to provide a better understanding of the present application. However, one skilled in the art will readily recognize that some of the features may be omitted, or replaced by other elements, materials, or methods in different situations. In some instances, some operations associated with the present application have not been shown or described in the specification to avoid obscuring the core portions of the present application, and may not be necessary for a person skilled in the art to describe in detail the relevant operations based on the description herein and the general knowledge of one skilled in the art.
Furthermore, the described features, operations, or characteristics of the description may be combined in any suitable manner in various embodiments. Also, various steps or acts in the method descriptions may be interchanged or modified in a manner apparent to those of ordinary skill in the art. Thus, the various orders in the description and drawings are for clarity of description of only certain embodiments, and are not meant to be required orders unless otherwise indicated.
The numbering of the components itself, e.g. "first", "second", etc., is used herein merely to distinguish between the described objects and does not have any sequential or technical meaning. The terms "coupled" and "connected," as used herein, are intended to encompass both direct and indirect coupling (coupling), unless otherwise indicated.
The application provides a nano metal coating 1 for a current collector base film, wherein the nano metal coating 1 comprises the following components in percentage by mass:
0.3-1% of metal nano particles, 0.02-2% of adhesive, 0.1-1% of surfactant, 0.5-5% of dispersing agent and the balance of solvent.
Wherein the metal nanoparticles are the main body of the coating; the adhesive is used for providing basic adhesive force for the metal nano coating; the surfactant plays a role in wetting, and reduces the surface tension of the solvent, so that the coating can be better attached to the surface of the substrate during coating; the dispersing agent can uniformly disperse the metal nano particles in the solvent, so that the uniformity of the distribution of the metal nano particles on the substrate can be improved during coating; the solvent is water, so that each component can be dissolved or dispersed in the solvent, fluidity is provided for the slurry of the nano metal coating, and the solvent can be evaporated after the nano metal coating is dried and solidified.
In an alternative example, the metal nanoparticles may be, but are not limited to, nano silver or nano copper having a particle size of 40-80nm, and illustratively, nano silver of 40nm, 60nm and 80nm, or nano copper of 40nm, 60nm and 80nm may be selected.
In an alternative example, the adhesive is a component that has tackiness and does not react with other substances in the nano-metal coating, for example, the adhesive may be, but is not limited to, one or more of sodium hydroxymethyl cellulose and polyacrylic acid; the surfactant can be one or more of sodium dodecyl benzene sulfonate, polyhydroxy ammonium polyacrylate and ethylene oxide polymer; the dispersant may be, but is not limited to, one or more of polyvinylpyrrolidone, ethylene glycol and isopropanol.
The nano-metal coating 1 disclosed herein may be applied in a current collector of a battery, for example, it may be coated on a current collector base film of a lithium battery.
The application further provides a composite current collector base film, as shown in fig. 1, which comprises the nano metal coating 1 and a polyolefin base material 2, wherein the nano metal coating 1 is attached to two opposite side surfaces of the polyolefin base material 2; illustratively, taking the polyolefin substrate 2 placed horizontally as an example, the nano metal coating 1 may be applied to the upper and lower surfaces of the polyolefin substrate 2 by, but not limited to, doctor blade coating, meyer bar coating, gravure roll coating, spray coating, dip coating, etc.; in the embodiments disclosed herein, the thickness of the nano metal coating 1 is 30-110nm, for example, in some examples, the thickness of the nano metal coating 1 may be 30nm, 50nm, 70nm, 90nm, 110nm.
Illustratively, the polyolefin substrate 2 may be, but is not limited to, one or more composite structures of polypropylene and its derivatives, polyethylene and its derivatives, and copolymers of polypropylene and its derivatives and polyethylene and its derivatives, and further, the thickness of the polyolefin substrate 2 may be 3-8 μm, for example, the thickness of the polyolefin substrate 2 may be 3 μm, 5 μm or 8 μm.
The application further provides a composite current collector, which comprises the composite current collector base film, wherein a metal layer is loaded on at least one side surface of the composite current collector base film, and specifically, the metal layer can be deposited on the surface of the composite current collector base film through a magnetic sputtering technology; for example, the above composite current collector may be prepared by the following method:
transferring the composite current collector base film into a cavity of a magnetron sputtering machine;
at 10 -5 Under the vacuum condition of the support, bombarding a high-purity metal target by adopting argon gas, so that metal is gradually deposited on the surface of the composite current collector base film and is gradually thickened, and the composite current collector is prepared; in a specific example, the metal layer may be, but is not limited to, metallic copper and metallic aluminum, and the corresponding metal target is a pure copper target or a pure aluminum target.
The nano-metal coating 1 disclosed in the present application can be excellently attached to the surface of the polyolefin substrate 2; the nano metal has strong polarity and good conductivity, so that after nano metal particles are introduced into the surface of the polyolefin substrate 2, the conductivity of the polyolefin substrate 2 can be improved, and on the other hand, the polarity of the polyolefin substrate 2 is improved, and the prepared composite current collector substrate film is beneficial to the effective deposition of a metal layer in the composite current collector process, and the adhesive force of the metal layer on the composite current collector substrate film is greatly improved.
For better illustration of the effects achieved by the present application, the present application further provides the following more specific embodiments:
in the following examples, the polyolefin substrate 2 used is commercially available from polypropylene films on the market; the metal nanoparticles are obtained by commercially available metal nanoparticles or by conventional methods for producing metal nanoparticles (for example, the method can be used for production as disclosed in chinese patent documents such as CN201610333019.7 and CN 201810982155.8).
Example 1:
in the embodiment, a biaxially oriented polypropylene film with a thickness of 6 μm is used as a base material; the polypropylene substrate is coated on both sides with a nano-metal coating 1.
The slurry of the nano metal coating 1 comprises the following components in percentage by mass: 0.5% of nano copper particles, 0.05% of sodium hydroxymethyl cellulose, 0.5% of polyhydroxy ammonium polyacrylate, 0.6% of polyvinylpyrrolidone and the balance of deionized water are used as solvents. Fig. 2 shows an SEM image of nano-copper particles used in the nano-metal coating 1.
The slurry is coated on the upper and lower surfaces of a polypropylene substrate by a dip coating method, wherein the thickness of the cured coating is 60nm, and then the coating is annealed for 3 minutes at 110 ℃ to obtain a composite current collector base film which is denoted as P1.
Transferring the prepared composite current collector base film into a magnetron sputtering machine, multiplying copper on the surface of the composite current collector base film and gradually thickening to form a copper layer with the thickness of 200nm, and obtaining the composite current collector which is named as PU1.
Example 2
In the embodiment, a biaxially oriented polypropylene film with a thickness of 6 μm is used as a base material; the polypropylene substrate is coated on both sides with a nano-metal coating 1.
The slurry of the nano metal coating 1 comprises the following components in percentage by mass: 1% of nano copper particles, 0.05% of sodium hydroxymethyl cellulose, 0.5% of polyhydroxy ammonium polyacrylate, 0.6% of polyvinylpyrrolidone and the balance of deionized water as solvents.
The slurry is coated on the upper and lower surfaces of a polypropylene substrate by a dip coating method, wherein the thickness of the cured coating is 60nm, and then the coating is annealed for 3 minutes at 110 ℃ to obtain a composite current collector base film which is denoted as P2.
Transferring the prepared composite current collector base film into a magnetron sputtering machine, multiplying copper on the surface of the composite current collector base film and gradually thickening to form a copper layer with the thickness of 200nm, and obtaining the composite current collector which is named as PU2.
Example 3
In the embodiment, a biaxially oriented polypropylene film with a thickness of 6 μm is used as a base material; the polypropylene substrate is coated on both sides with a nano-metal coating 1.
The slurry of the nano metal coating 1 comprises the following components in percentage by mass: 0.5% of nano copper particles, 0.05% of sodium hydroxymethyl cellulose, 0.5% of polyhydroxy ammonium polyacrylate, 1% of polyvinylpyrrolidone and the balance of deionized water are used as solvents.
The slurry is coated on the upper and lower surfaces of a polypropylene substrate by a dip coating method, wherein the thickness of the cured coating is 60nm, and then the coating is annealed for 3 minutes at 110 ℃ to obtain a composite current collector base film which is denoted as P3.
Transferring the prepared composite current collector base film into a magnetron sputtering machine, multiplying copper on the surface of the composite current collector base film and gradually thickening to form a copper layer with the thickness of 200nm, and obtaining the composite current collector which is named as PU3.
Example 4
In the embodiment, a biaxially oriented polypropylene film with a thickness of 6 μm is used as a base material; the polypropylene substrate is coated on both sides with a nano-metal coating 1.
The slurry of the nano metal coating 1 comprises the following components in percentage by mass: 0.5% of nano silver particles, 0.05% of sodium hydroxymethyl cellulose, 0.5% of polyhydroxy ammonium polyacrylate, 0.6% of polyvinylpyrrolidone and the balance of deionized water are used as solvents.
The slurry is coated on the upper and lower surfaces of a polypropylene substrate by a dip coating method, wherein the thickness of the cured coating is 60nm, and then the coating is annealed for 3 minutes at 110 ℃ to obtain a composite current collector base film which is denoted as P4.
Transferring the prepared composite current collector base film into a magnetron sputtering machine, multiplying silver on the surface of the composite current collector base film and gradually thickening to form a silver layer with the thickness of 200nm, and obtaining the composite current collector which is named as PU4.
Comparative example 1
The comparative example uses a biaxially oriented polypropylene film having a thickness of 6 μm as a base material; the polypropylene substrate is coated on both sides with a nano-metal coating 1.
The slurry of the nano metal coating 1 comprises the following components in percentage by mass: 0.5% of nano copper particles, 0.05% of sodium hydroxymethyl cellulose, 0.5% of polyhydroxy ammonium polyacrylate and the balance of deionized water are used as solvents.
The slurry was coated on the upper and lower surfaces of the polypropylene base material by dip coating, wherein the thickness of the coating after curing was 60nm, and then annealed at 110 degrees centigrade for 3 minutes to obtain a control base film, designated as D1.
The control base film thus obtained was transferred to a magnetron sputtering machine, and copper was deposited on the surface of the control base film and gradually thickened to form a copper layer having a thickness of 200nm, to obtain a control film, which was designated as CU1.
Comparative example 2
The comparative example uses a biaxially oriented polypropylene film having a thickness of 6 μm as a base material; and the polypropylene substrate was double-sided uncoated with nano-metal coating 1, designated as D2.
The obtained polypropylene film was transferred to a magnetron sputtering machine, copper was deposited on the surface of the polypropylene film and gradually thickened to form a copper layer having a thickness of 200nm, and a film for control was obtained and designated as CU2.
Example 5
The composite current collectors prepared in examples 1 to 4 and the films for control prepared in comparative examples 1 and 2 were tested for various properties.
The adhesive force is tested according to the hundred-cell test method described in GB9286-2021, and the method specifically comprises the following steps: dividing the test film into 100 small squares with the size of 1x1mm, tightly adhering the film by using an adhesive tape, vertically stripping the adhesive tape, and observing the detachment condition of an additional layer in each square; the sheet resistance is tested by a four-probe tester with a round head to verify the conductivity of the composite current collector. The specific test results are shown in table 1:
TABLE 1
| Project | Base film | Square resistance (omega/≡) | Composite current collector | Square resistance (omega/≡) | Percent abscission/% |
| Example 1 | P1 | 89 | PU1 | 23 | 6 |
| Example 2 | P2 | 52 | PU2 | 16 | 8 |
| Example 3 | P3 | 47 | PU3 | 10 | 2 |
| Example 4 | P4 | 43 | PU4 | 8 | 5 |
| Comparative example 1 | D1 | 104 | CU1 | 62 | 23 |
| Comparative example 2 | D2 | Non-conductive | CU2 | 4200 | All fall off |
As can be seen from Table 1, the polypropylene film D1 without any coating in comparative example 2 does not have conductivity per se, and the sheet resistance values of the polypropylene substrates P1 to P4 coated with the nano metal coating 1 prepared by the method are all greatly improved, which indicates that the nano metal coating 1 disclosed in the application can endow the polyolefin substrate 2 with conductivity after being coated on the polyolefin substrate 2.
D1 provided in comparative example 1, which was coated with a nano metal coating 1 lacking a dispersant on a polyolefin substrate 2, was able to impart a certain conductivity to the substrate, but had a higher sheet resistance value; however, after the metal layer is deposited by using the substrate through magnetic sputtering, the adhesion of the metal layer is poor in the hundred grid test, and the falling rate is up to 23%.
As can be seen from PU1 to PU4 in table 1, the sheet resistance of the composite current collector prepared by metal deposition from the polyolefin substrate 2 coated with the nano metal coating 1 disclosed in the present application was further reduced, and the adhesion of the metal layer was excellent in the hundred-cell test.
Therefore, the nano metal coating 1 disclosed by the application has good adhesive force and can enhance the adhesive force of the metal layer on the substrate; the composite current collector base film attached with the nano metal coating 1 has good conductivity; the nano metal coating 1 and the composite current collector base film attached with the nano metal coating 1 have wide application prospects in the field of secondary batteries as current collectors.
The foregoing description of the invention has been presented for purposes of illustration and description, and is not intended to be limiting. Several simple deductions, modifications or substitutions may also be made by a person skilled in the art to which the invention pertains, based on the idea of the invention.
Claims (10)
1. The nano metal coating for the current collector base film is characterized by comprising the following components in parts by mass:
0.3-1 part of metal nano particles, 0.02-2 parts of adhesive, 0.1-1 part of surfactant and 0.5-5 parts of dispersing agent.
2. The nano-metal coating for a current collector substrate film according to claim 1, wherein the metal nano-particles are nano-silver or nano-copper.
3. The nano-metal coating for a current collector substrate film according to claim 2, wherein the metal nano-particles have a particle size of 40-80nm.
4. A nano metal coating for a current collector base film according to any one of claims 1 to 3, wherein the binder is one or more of sodium hydroxymethyl cellulose and polyacrylic acid; and/or
The surfactant is one or more of sodium dodecyl benzene sulfonate, polyhydroxy ammonium polyacrylate and ethylene oxide polymer; and/or
The dispersing agent is one or more of polyvinylpyrrolidone, ethylene glycol and isopropanol.
5. Use of a nano-metal coating according to any one of claims 1 to 4 in a current collector.
6. A composite current collector substrate film comprising a nano-metal coating according to any one of claims 1 to 4; and
a polyolefin substrate, the nano-metal coating being attached to opposite side surfaces of the polyolefin substrate.
7. The composite current collector substrate film according to claim 6, wherein the polyolefin substrate is a composite structure of one or more of polypropylene and its derivatives, polyethylene and its derivatives, and copolymers of polypropylene and its derivatives and polyethylene and its derivatives.
8. The composite current collector substrate film of claim 6, wherein the polyolefin substrate has a thickness of 3 to 8 μm.
9. The composite current collector substrate film of claim 6, wherein the nano-metal coating has a thickness of 30-110nm.
10. A composite current collector comprising a composite current collector base film according to any one of claims 6 to 9; and
and the metal layer is deposited on at least one side surface of the composite current collector base film.
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