CN108531876A - A kind of coating process flow for lithium battery collector - Google Patents
A kind of coating process flow for lithium battery collector Download PDFInfo
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- CN108531876A CN108531876A CN201810249903.1A CN201810249903A CN108531876A CN 108531876 A CN108531876 A CN 108531876A CN 201810249903 A CN201810249903 A CN 201810249903A CN 108531876 A CN108531876 A CN 108531876A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of coating process flows for lithium battery collector, it is metal-coated membrane on 15 microns of Ultrathin substrates below that it, which is in thickness, to obtain the coated product for having and bonding force can be improved, its technological process is as follows, pre-treatment first is carried out to Ultrathin substrate surface, a kind of base material for having and bonding force substrate can be improved is formed, using 5 50nm of magnetic control film coating, then 600 1000nm of water plating；Or first use 5 50nm of magnetic control film coating, then 100 700nm of evaporation coating, last 100 800nm of water plating.Film plating layer bonding force on the base material of the present invention is stronger and keeps the performance of lithium battery collector more stable, the lithium ion battery energy density bigger obtained.
Description
Technical field
The present invention relates to base material plated film fields, and in particular to a kind of coating process flow for lithium battery collector.
Background technology
With the development of modern industrial technology, base material plated film demand is increasing.Base material plated film not only has hard substrates
The photoelectric characteristic of film, and have many advantages, such as it is light-weight, foldable, non-breakable, be readily transported, equipment investment it is few, it is extensive
Applied to fields such as high-performing car pad pasting, plasm TV FPD, touch screen, solar cells.It is answered according to different
It is also different to the Functional Requirement of institute's film plating layer with demand, but generally, Functional Requirement of the every profession and trade to base material film at present
Have the tendency that higher and higher, film structure also tends to become increasingly complex.
Evaporation coating provides heat source using thermal resistance evaporation source, makes low melting point evaporation material fusing, and evaporation or distillation, which become, steams
Vapour atom is then deposited into matrix surface and forms film layer, has rate of film build fast, the advantages such as production cost is low, optical thin film,
The preparation of thermal protection coating and erosion shield is with a wide range of applications.But the film layer that thermal evaporation techniques obtain is thicker
It is rough, the poor bonding strength of film layer and matrix, and it is readily formed coarse columnar crystal structure and higher porosity, to film
Corrosion-resistant and antioxygenic property it is quite unfavorable.
Magnetron sputtering technique (magnetic control film coating) carries out plated film, i.e. argon ion bombardment target material surface using cathodic sputtering principle,
The atomic deposition sputtered forms a film to matrix surface.The preparation of large area uniform film layer, thicknesses of layers may be implemented in magnetron sputtering
It is easy to accurately control with composition, film layer structure compactness is good, and the film layer adhesive strength of acquisition is 10 times of general thermal evaporation plated film
More than, but magnetron sputtering technique but has that deposition rate is slow, causes low production efficiency and problem of high cost.
Water plates, and is general electroplate liquid plating.It is the needs for various ontologies and coating, water distribution plating solution is plated
Part is placed in water plating solution, makees weak vibrations, and (such as silver-plated, it is only necessary to 30 seconds) can be completed in a relatively short period of time.In substrate surface
Anticorrosion, wear-resisting, anti-scratch and beautiful appearance decoration functions can be reached by implementing metallization electroplating technology, therefore open up base material
Application range.But this traditional electroplating technology pre-treatment (such as containing electrochemical deoiling cleaning, roughening, neutralize, sensitization, change
Learn each process such as nickel plating) a large amount of sewage discharge is caused, very not environmentally.
It includes following that Chinese patent literature CN104087933B, which discloses a kind of film plating process and its device, the film plating process,
Step：At least one layer of vacuum nano film layer is formed using vacuum coating mode to plated base material；In vacuum nano film layer
Surface forms at least one layer of air nanometer thin film layer using air plated film mode.The air plated film mode is spraying plating, the quilt
It is sapphire substrate or aluminosilicate glass to plate base material；The vacuum nano film layer is aluminium oxide and/or silica, overall thickness 5-
8nm；The air nanometer thin film layer is fluorine containing silane, overall thickness 1-3nm.Wherein, vacuum coating mode includes magnetron sputtering
Plated film, thermal evaporation plated film, electronics gun-type plated film or multi-arc ion plating film carry out vacuum coating to base material and may be used therein one
Kind is a variety of, and it may be multilayer to be formed by vacuum nano film layer, and overall thickness is more than 5nm.Air plated film mode packet
Spraying plating, roller plating or immersion plating plated film are included, can be used simultaneously when plated film one such or a variety of.Vacuum bottoming film plating layer will be coated with
Base material is transferred in air, is coated with one or more layers air nano thin-film again on prime coat, and overall thickness is more than 1nm.
For CN104087933B in a first aspect, base material mainly is sapphire substrate or aluminosilicate glass, these base materials are general
It is to be used without the base material of the positive or negative collector in aluminum cell.Such as sapphire is used for making white/blue green light LED light
Critical material；And aluminosilicate glass is commonly used to make mobile phone screen cover plate material etc..
The air nanometer thin film layer of second aspect, film plating process plating is fluorine containing silane, and in the positive or negative collection of lithium battery
In the application of fluid, generally without the coating of fluorine containing silane, this is because fluorine containing silane is generally used for the self-cleaning of glass product,
The low index of refraction of fluorine containing silane can enable glass baseplate act the effect for preventing light from reflecting.Or fluorine containing silane has hydrophobicity and makees
It is used for hydrophobic plated film.This two kinds of properties of fluorine containing silane can not be used as the coating of the positive or negative collector of lithium battery；
The third aspect, thickness summation are generally 6-11nm.In the positive or negative collector of lithium battery, the thickness of each coating
It is very big on the influence of the performance of product, it has been typically necessary more suitable coating range, can just make the positive or negative afflux of lithium battery
Body obtains stable performance.In the application of the positive or negative collector of lithium battery, general is not thickness range 6-11nm, the thickness model
Enclosing 6-11nm also can make its coating sheet resistance larger, and generate the adverse effect to battery performance.
Therefore, although CN104087933B discloses the combination of different plated film modes, upper, base is applied in specific field
The selection of the thickness of material, the property of coating and coating is multifarious, can not simply release another from a field
The application in field, it is still necessary to pay performing creative labour in specific different application field.
Invention content
Therefore, to overcome above-mentioned technical problem, the purpose of the present invention is to provide a kind of platings for lithium battery collector
Membrane process flow so that it produces relatively stable and more superperformance lithium battery collector.
Used technical solution is：
A kind of coating process flow for lithium battery collector is metal-coated membrane on Ultrathin substrate, to be had
The coated product of bonding force can be improved, technological process is as follows, and magnetic control film coating 5-50nm, then water are first used on Ultrathin substrate surface
Plating 600-1000nm；Or technological process is as follows, first uses magnetic control film coating 5-50nm on Ultrathin substrate surface, then evaporates
Plated film 100-700nm, last water plating 100-800nm.
Preferably, the Ultrathin substrate is macromolecule membrane base material, super thin fiber paper base material, graphite paper base material, nanometer paper
Or macromolecule and fiber composite ultrathin film base material.
Preferably, the Ultrathin substrate thickness is 15 microns or less.
Preferably, magnetic control film coating 10nm, then water plating 800nm are first used；Or magnetic control film coating 10nm is first used, then
Evaporation coating 200nm, last water plating 700nm.
Preferably, the sheet resistance of the metal film plated on base material is 10-30 milliohms.
Preferably, pre-treatment is carried out to substrate surface, while Ni film 5-50nm is plated using magnetic control, formation one kind has high viscous
The base material of resultant force substrate.
Preferably, pre-treatment is carried out to substrate surface, while uses magnetic control alloy plating film 5-50nm, using acid or alkali to mistake
It crosses layer to be handled, forms a kind of base material with high adhesion substrate.
Preferably, the method for carrying out pre-treatment to substrate surface is that it includes mechanical treatment, chemical treatment, surface first to use
It is one or more in substrate surface shape in modifier treatment, flame treatment, corona treatment, surface grafting and surface coating
At porous structure, then using the surface modifier immersed substrate surface for containing organic-philic group and close inorganic group simultaneously
The beneficial effects of the present invention are：
In the application of specific lithium battery collector, base material, the property (coat of metal) of coating and the thickness model of coating
It is a preferable selection combination to enclose, and on this basis, the bonding force of film layer has obtained most between magnetic control film coating and water plating
Good performance embodies, and bonding force will be high than others selection combination.
When metal coating contains copper coating, you can the negative collector as lithium battery；When metal coating contains electroplated aluminum
When layer, you can the positive collector as lithium battery.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only the preferred embodiment of the invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without creative efforts belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of coating process flow for lithium battery collector is the metal-coated membrane on super thin fiber paper base material, base
Material thickness is 10 microns.When metal-coated membrane, magnetic control is first used to plate Zn film 10nm, then water plating plating Cu films 800nm.
Embodiment 2
A kind of coating process flow for lithium battery collector, is the metal-coated membrane on graphite paper base material, and base material is thick
Degree is 10 microns.When metal-coated membrane, magnetic control is first used to plate Zn film 10nm, then water plating plating Cu films 800nm.
Embodiment 3
A kind of coating process flow for lithium battery collector, is the metal-coated membrane on nanometer paper base material, and base material is thick
Degree is 10 microns.When metal-coated membrane, magnetic control is first used to plate Zn film 10nm, then water plating plating Cu films 800nm.
Embodiment 4
A kind of coating process flow for lithium battery collector is on macromolecule membrane base material (such as PET base material)
Metal-coated membrane, base material thickness are 3 microns.When metal-coated membrane, first magnetic control is used to plate Zn film 5nm, then evaporation plating Cu film 100nm,
Last water plating plating Ni films 500nm.
Embodiment 5
A kind of coating process flow for lithium battery collector is the metal-coated membrane on macromolecule membrane base material, base
Material thickness is 6 microns.When metal-coated membrane, first magnetic control is used to plate Sn film 10nm, then evaporation plating Cu films 200nm, last water plating plating
Ti films 700nm.
Embodiment 6
A kind of coating process flow for lithium battery collector is the metal-coated membrane on macromolecule membrane base material, base
Material thickness is 15 microns.When metal-coated membrane, first magnetic control is used to plate Ni film 10nm, then evaporation plating Al films 300nm, last water plating plating
Ni films 200nm.
Embodiment 7
A kind of coating process flow for lithium battery collector is the metal-coated membrane on macromolecule membrane base material, base
Material thickness is 15 microns.Sandblast technology (mechanical treatment) is first used to form porous structure in substrate surface, then use has containing parent
The surface modifier immersed substrate surface of machine group and close inorganic group.It is first adopted in the substrate surface metal-coated membrane of porous structure
Ni film 10nm are plated with magnetic control, transition zone is handled using acid or alkali, then evaporation plating Al films 300nm, last water plating plating Ni
Film 200nm.
Embodiment 8
A kind of coating process flow for lithium battery collector is the metal-coated membrane on macromolecule membrane base material, base
Material thickness is 15 microns.It first uses sandblast technology to form porous structure in substrate surface, then uses and contain organic-philic group and parent
The surface modifier immersed substrate surface of inorganic group.First magnetic control is used to plate in the substrate surface metal-coated membrane of porous structure
ZnNi alloy film 10nm are handled transition zone using acid or alkali, then evaporation plating Al films 300nm, last water plating plating Ni films
200nm。
Comparative example 1
A kind of coating process flow for lithium battery collector, is the metal-coated membrane on nanometer paper base material, and base material is thick
Degree is 3 microns.When metal-coated membrane, first magnetic control is used to plate Zn film 3nm, then evaporation plating Cu films 80nm, last water plating plating Ni films
700nm。
Comparative example 2
A kind of coating process flow for lithium battery collector, is the metal-coated membrane on nanometer paper base material, and base material is thick
Degree is 11 microns.When metal-coated membrane, first magnetic control is used to plate Ni film 60nm, then evaporation plating Al films 700nm, last water plating plating Ni films
50nm。
Comparative example 3
A kind of coating process flow for lithium battery collector is the metal-coated membrane on macromolecule membrane base material, base
Material thickness is 16 microns.When metal-coated membrane, first magnetic control is used to plate Ni film 10nm, then evaporation plating Al films 300nm, last water plating plating
Ni films 200nm.
Embodiment 1-8 is tested, the bonding force for obtaining the film plating layer and base material on base material is stronger, than nonmetallic plated film
And non-paper substrates plated film, on-macromolecular film substrate plated film all improve at least 50%, the especially bonding of embodiment 4-6
Power is more stronger than the bonding force of embodiment 1-3, and optimal is embodiment 4, and the amplitude of raising is maximum.
Comparative example 1-2 is tested, the bonding force of film plating layer and base material on the base material of comparative example 1-2 compares embodiment
The bonding force of film plating layer and base material on 1-4 base materials is intended to low.
Comparative example 3 is tested, the energy density of the product of comparative example 3 will be less than embodiment 1-8,4 product of embodiment
Energy density improve at least 10% than the energy density of 3 product of comparative example, have raising by a relatively large margin, illustrate Ultrathin substrate
Optimal thickness is 15 microns or less.
The sheet resistance of the metal film of embodiment 1-8 is 10-30 milliohms, this sheet resistance has preferably the battery of lithium battery collector
Stabilization.
Embodiment 7 is that the metal of one layer of 5-50nm is plated on substrate surface porous structure in order to further increase bonding force
If Ni is as transition zone, then plated film is carried out, can further improve 20% or more bonding force.
Embodiment 8 is porous structure to be formed in substrate surface, in the porous knot of substrate surface to further increase bonding force
The alloy of one layer of 5-50nm is plated on structure as transition zone, transition zone is handled using acid or alkali, then carry out plated film and can be improved
50% or more bonding force.
Embodiment 7-8 can improve the adhesive ability of plated film using surfactant.Macromolecule membrane and metal film it
Between play the role of promote bonding.Surfactant contains organic-philic group and close inorganic group simultaneously, and one end parent may be implemented
Organic (macromolecule membrane) one end parent is inorganic (metal film), to play the role of promoting bonding, improves bonding force.
The series of detailed descriptions listed above is illustrated only for possible embodiments of the invention,
They are all without departing from equivalent embodiment made by technical spirit of the present invention or change not to limit the scope of the invention
It should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of coating process flow for lithium battery collector, which is characterized in that it is metal-coated membrane on Ultrathin substrate, with
The coated product for having and bonding force can be improved is obtained, technological process is as follows, and magnetic control film coating 5- is first used on Ultrathin substrate surface
50nm, then water plating 600-1000nm；Or technological process is as follows, and magnetic control film coating 5- is first used on Ultrathin substrate surface
50nm, then evaporation coating 100-700nm, last water plating 100-800nm.
2. the coating process flow according to claim 1 for lithium battery collector, which is characterized in that the ultra-thin base
Material is macromolecule membrane base material, super thin fiber paper base material, graphite paper base material, nanometer paper or macromolecule and fiber composite ultrathin film
Base material.
3. the coating process flow according to claim 1 for lithium battery collector, which is characterized in that the ultra-thin base
Material thickness is 15 microns or less.
4. the coating process flow according to claim 1 for lithium battery collector, which is characterized in that first use magnetic control
Plated film 10nm, then water plating 800nm；Or magnetic control film coating 10nm is first used, then evaporation coating 200nm, last water plating is plated
Film 700nm.
5. the coating process flow according to claim 1 or 2 for lithium battery collector, which is characterized in that on base material
The sheet resistance of the metal film of plating is 10-30 milliohms.
6. the coating process flow according to claim 1 for lithium battery collector, which is characterized in that substrate surface
Pre-treatment is carried out, while N i film 5-50nm are plated using magnetic control, forms a kind of base material with high adhesion substrate.
7. the coating process flow according to claim 1 for lithium battery collector, which is characterized in that substrate surface
Pre-treatment is carried out, while using magnetic control alloy plating film 5-50nm, transition zone is handled using acid or alkali, forming one kind has
The base material of high adhesion substrate.
8. the coating process flow for lithium battery collector described according to claim 6 or 7, which is characterized in that base material
Surface carry out pre-treatment method be, first using include mechanical treatment, chemical treatment, surface modifier processing, flame treatment, etc.
It is one or more in substrate surface formation porous structure in gas ions processing, surface grafting and surface coating, then using simultaneously
Surface modifier immersed substrate surface containing organic-philic group and close inorganic group.
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| WO2023206687A1 (en) * | 2022-04-25 | 2023-11-02 | 江阴纳力新材料科技有限公司 | Composite current collector and preparation method therefor, and electrode plate and secondary battery |
| CN118572121A (en) * | 2024-05-16 | 2024-08-30 | 江苏英联复合集流体有限公司 | A positive and negative electrode fused foil material and a manufacturing method thereof |
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Application publication date: 20180914 |