CN116791035B - Preparation method of metal foil - Google Patents
Preparation method of metal foil Download PDFInfo
- Publication number
- CN116791035B CN116791035B CN202310792345.4A CN202310792345A CN116791035B CN 116791035 B CN116791035 B CN 116791035B CN 202310792345 A CN202310792345 A CN 202310792345A CN 116791035 B CN116791035 B CN 116791035B
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- metal layer
- metal
- metal foil
- organic film
- layer
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 177
- 239000002184 metal Substances 0.000 title claims abstract description 177
- 239000011888 foil Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000004544 sputter deposition Methods 0.000 claims abstract description 42
- 238000007747 plating Methods 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 230000008020 evaporation Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 12
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052737 gold Inorganic materials 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 238000007772 electroless plating Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 description 19
- 239000005020 polyethylene terephthalate Substances 0.000 description 19
- 238000012937 correction Methods 0.000 description 7
- 230000000875 corresponding effect Effects 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- -1 Polyethylene terephthalate Polymers 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005314 correlation function Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- 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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/542—Controlling the film thickness or evaporation rate
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/14—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using spraying techniques to apply the conductive material, e.g. vapour evaporation
- H05K3/146—By vapour deposition
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/14—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using spraying techniques to apply the conductive material, e.g. vapour evaporation
- H05K3/16—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using spraying techniques to apply the conductive material, e.g. vapour evaporation by cathodic sputtering
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a preparation method of a metal foil. The metal foil comprises a first metal layer, wherein the first metal layer is formed in any one of a film plating mode of vacuum sputtering, evaporation plating and chemical plating, and the film plating times N 1 and the average sheet resistance R of the first metal layer meet the following relation: r= (a/σ) N 1 ‑0.99. The embodiment of the invention can rapidly acquire the coating times of the metal foil, improve the production efficiency of the metal foil and reduce the production cost.
Description
Technical Field
The invention relates to the technical field of electronics, in particular to a preparation method of a metal foil.
Background
The negative electrode material structure of the existing lithium ion battery is a pure metal copper foil, the density of metal is large, and the thickness, the weight and the like of the metal copper foil are too large to facilitate the application of the new energy battery and improve the energy density of the new energy battery. By adopting PET (Polyethylene terephthalate) and other organic films as the support, the metal foil formed by the conductive layers is arranged on two sides, and the thickness and the density of the common PET organic film are far smaller than those of metal, so that the thickness and the weight of the whole metal foil can be greatly reduced, and the energy density of the PET organic film can be improved when the PET organic film is applied to new energy batteries.
In the actual production process, a metal layer is formed on the PET film by using the processes of evaporation, sputtering, electroplating and the like, the thickness of the metal layer cannot be accurately measured by conventional detection equipment, the thickness parameter of the ultrathin film material has high requirements on the measurement equipment and the process is complex, and the thickness and sheet resistance are found to be substandard through complex tests, so that the equipment and the process are adjusted and corrected to obtain the expected metal foil. In the specific actual production, the process is time-consuming and labor-consuming and has low production efficiency.
Disclosure of Invention
The invention provides a preparation method of a metal foil, which can rapidly obtain the coating times of the metal foil, improve the production efficiency of the metal foil and reduce the production cost.
According to an aspect of the present invention, there is provided a method for preparing a metal foil, the metal foil including a first metal layer, the first metal layer being formed by any one of vacuum sputtering, evaporation plating and electroless plating, the number of plating times N 1 and an average sheet resistance R of the first metal layer satisfying the following relation:
R(A/)*N1 -0.99
Wherein the value range of A is 1700-2400, sigma is the conductivity of the first metal layer, the unit is 1/(m), the coating frequency N 1 is more than or equal to 1, and N 1 is a positive integer, and the unit of the average square resistance R is .
Optionally, the metal foil further includes an organic film layer, and a side surface of the organic film layer is in contact with the first metal layer.
Optionally, the material of the organic film layer includes one of PET, PP, and PI;
Optionally, the material of the organic film layer includes PET, and the thickness of the organic film layer is 1 m to 60 m.
Optionally, the material of the first metal layer is one of copper, aluminum, nickel, chromium, zinc, silver, gold and titanium, or an alloy of at least two metals of copper, aluminum, nickel, chromium, zinc, silver, gold and titanium.
Optionally, the average thickness d of the first metal layer and the average sheet resistance R of the first metal layer satisfy the following relation:
RB*d-1.082
wherein the unit of the average thickness d is nm, and the value range of B is 200-260.
Optionally, the first metal layer is disposed on a side surface of the organic film layer by vacuum sputtering, and the relationship between the average thickness d of the first metal layer and the number of vacuum sputtering times N 2 is:
dC*N2+1.9038
Wherein the number of times of vacuum sputtering N 2 is more than or equal to 1, N 2 is a positive integer, the average thickness d is nm, and the range of C is 7.5-9.5.
Optionally, the current of the vacuum sputtering is between 5 and 9A; and/or the number of the groups of groups,
The vacuum sputtering voltage is between 1000 and 1500V.
Optionally, the two opposite sides of the organic film layer are respectively provided with the first metal layers, and the two first metal layers are respectively arranged on the surface of the organic film layer in any one of a vacuum sputtering, an evaporation plating and a chemical plating manner.
Optionally, the metal foil further includes a second metal layer, where the second metal layer is disposed on a surface of the first metal layer away from the organic film layer.
Optionally, the material of the second metal layer is one of copper, aluminum, nickel, chromium, zinc, silver, gold and titanium, or an alloy containing at least two metals of copper, aluminum, nickel, chromium, zinc, silver, gold and titanium.
Optionally, the thickness of the second metal layer is 0.5 m to 60 m.
The roughness of the surface of the second metal layer away from the first metal layer is 1.1-2.5 mu m.
According to another aspect of the invention, a printed circuit board is provided, and the metal foil manufactured by the method for manufacturing the metal foil according to any embodiment of the invention is used for circuit printing.
According to another aspect of the invention, a lithium ion battery is provided, and the metal foil is manufactured by the method for manufacturing the metal foil according to any embodiment of the invention.
According to the embodiment of the invention, the correlation function between the average sheet resistance and the coating times of the metal layer of the metal foil is obtained by establishing the relation between the average sheet resistance and the coating times, and the coating times can be quickly obtained according to the metal foil sample requirement of a certain sheet resistance value preset by a customer through the function, so that the optimal and reasonable times of coating can be conveniently determined, the production efficiency is improved, and the production cost is reduced.
It should be understood that the description in this section is not intended to identify key or critical features of the embodiments of the invention or to delineate the scope of the invention. Other features of the present invention will become apparent from the description that follows.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view of a metal foil according to an embodiment of the present invention;
FIG. 2 is a graph showing the average thickness and the average sheet resistance of the first metal layer;
FIG. 3 is a graph showing the relationship between the number of sputtering and the average thickness of the first metal layer;
FIG. 4 is a schematic illustration of yet another metal foil provided by an embodiment of the present invention;
fig. 5 is a schematic view of yet another metal foil provided by an embodiment of the present invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The embodiment of the invention provides a metal foil, which comprises a first metal layer, wherein the first metal layer is formed by any one of coating modes of vacuum sputtering, evaporation coating and chemical plating, and the number of coating times N 1 and the average sheet resistance R of the first metal layer meet the following relational expression:
R(A/)*N1 -0.99
Wherein, the value range of A is 1700-2400, sigma is the conductivity of the first metal layer, the unit is 1/(m), the coating times N 1 is more than or equal to 1, and N 1 is a positive integer, and the unit of the average square resistance R is .
Wherein, the parameter A can be adjusted according to a specific coating process. Further, the correlation coefficient R 2 of the above relation may have a value ranging from 0.995 to 0.999, for example, the correlation coefficient may be 0.997.
According to the embodiment of the invention, the relation between the average sheet resistance of the first metal layer in the metal foil and the plating times is established, so that the correlation function between the average sheet resistance and the plating times is obtained, and the plating times can be quickly obtained according to the metal foil sample requirement of a certain sheet resistance preset by a customer, so that the optimal and reasonable times of plating can be conveniently determined, the production efficiency is improved, and the production cost is reduced.
Fig. 1 is a schematic structural diagram of a metal foil according to an embodiment of the present invention, and optionally, referring to fig. 1, the metal foil further includes an organic film layer 20, and one side surface of the organic film layer 20 is in contact with the first metal layer 10.
Specifically, the first metal layer 10 is directly formed on the side surface of the organic film layer 20, and since the thickness and the density of the organic film layer 20 are far smaller than those of metal, the organic film layer 20 plays a supporting role in the metal foil, and the first metal layer 10 is arranged on the organic film layer 20 to form the metal foil, so that the thickness and the weight of the whole metal foil can be greatly reduced, and when the novel energy battery is applied to the novel energy battery, the novel energy battery can be favorably improved in energy density.
Optionally, the material of the organic film layer includes one of PET (Polyethylene Terephthalate ), PP (polypropylene), and PI (polyimide).
The PET, the PP and the PI have good flexibility, the density is small, the extensibility is good, the flexibility of the metal foil can be improved by adopting the PET, the PP and the PI, and the thickness and the weight of the metal foil are reduced. In addition, the material adopted by the organic film layer can also be PS (Polystyrene ), ABF (Acrylonitrile-Butadiene-Styrene Terpolymer), polyacrylamide/styrene sulfate terpolymer, BT resin, polyacrylic acid or polyurethane, etc.
Optionally, the material of the organic film layer 20 includes PET, and the thickness of the organic film layer is 1 m to 60 m.
Specifically, the organic film layer 20 is made of PET, which is beneficial to reducing the thickness of the whole PET metal foil and improving the energy density of the PET metal foil applied to the new energy battery. The thickness of the organic film layer 20 may be 3.5 m, 4.5 m, 5 m, 6 m, 10 m, 20 m, 30 m, 50 m, etc. by way of example.
Alternatively, the material of the first metal layer 10 is copper, aluminum, nickel, chromium, zinc, silver, gold, titanium, cobalt, tungsten, or other conductive metal, or an alloy of at least two metals of copper, aluminum, nickel, chromium, zinc, silver, gold, and titanium.
Specifically, the metal foil adopting the metal material can be used as a chip packaging material, a battery cathode material, a battery anode material and the like, and the plating times of different metals can be rapidly obtained according to the different conductivities of the different metals, so that the test times are reduced, and the working efficiency is improved.
Optionally, the average thickness d of the first metal layer 10 and the average sheet resistance R of the first metal layer 10 satisfy the following relation:
RB*d-1.082
wherein the unit of the average thickness d is nm, and the value range of B is 200-260.
Specifically, B is a correction coefficient, and the correction coefficient B can be adjusted according to an actual film plating process, so that the corresponding relationship between the sheet resistance and the average thickness is more accurate. By the above relation between the sheet resistance and the thickness of the first metal layer 10, it is advantageous to estimate the thickness of the product by simply testing the sheet resistance. Meanwhile, the balance between the optimal sheet resistance and the thickness is conveniently adjusted by a technician according to the functional relation, so that the optimal production scheme and process are facilitated to be optimized, the production efficiency is improved, and the cost is reduced.
Optionally, the first metal layer 10 is disposed on one side of the organic film layer 20 by vacuum sputtering, and the relationship between the average thickness d of the first metal layer 10 and the number of vacuum sputtering times N 2 is:
dC*N2+1.9038
Wherein the number of times of vacuum sputtering N 2 is more than or equal to 1, N 2 is a positive integer, the average thickness d is nm, and the range of C is 7.5-9.5.
Specifically, C is a correction coefficient, and the correction coefficient C can be adjusted according to the process parameters of the actual sputtering process, so that the corresponding relationship between the sputtering times and the average thickness is more accurate. Through the function, the thickness of the corresponding first metal layer 10 can be predicted through the sputtering times, so that the experiment times and production errors are reduced, the working efficiency and the product quality can be greatly improved, and the production cost is reduced.
In one embodiment, the current for vacuum sputtering is between 5-9A.
Further, the vacuum sputtering voltage is between 1000 and 1500V.
Specifically, the current of vacuum sputtering can be set between 5 and 9A, or the voltage of vacuum sputtering can be set between 1000 and 1500V, or the current of vacuum sputtering can be set between 5 and 9A, and the voltage of vacuum sputtering can be set between 1000 and 1500V.
The sputtering process conditions are limited, namely, the current parameters, the voltage parameters or the voltage and current parameters are limited, so that the sputtering efficiency can be improved, and the product quality can be improved.
In one embodiment, the organic film layer is plasma treated with argon at a flow rate of 30-190sccm prior to the vacuum sputtering process. By adopting the argon plasma treatment, the surface of the PET film can be cleaned, the surface unevenness of the PET film can be increased, the bonding surface area can be increased, and the bonding force between the first metal layer and the surface of the PET film can be improved.
The following describes the use process of the functional relationship between the average square resistance R of the first metal layer and the number of coating times N 1 in combination with a specific metal foil structure:
the thickness detection method comprises the following steps: the thickness was measured using a step meter and the average value was taken as the average thickness by testing at least 6 points.
The sheet resistance detection method comprises the following steps: four probes Fang Zuyi are adopted, and a four-probe method is adopted to measure the sheet resistance of the film, and the average value is obtained after the sheet resistance of any six position points is measured as the average square resistance due to the small sample area.
In vacuum sputtering coating equipment, nickel-chromium alloy is adopted as a target material, sputtering is carried out on a PET substrate in a magnetron sputtering mode, the average value of sheet resistances of the corresponding sputtering times is recorded by counting different sputtering times, and at least 6 groups of data are tested to obtain a functional relation. The first metal layer thickness and the number of measurements of the first resistance are shown in table 1.
TABLE 1
Fig. 2 is a graph showing the relationship between the average thickness and the average sheet resistance of the first metal layer 10, and fig. 2 is drawn according to the data shown in table 1, and referring to fig. 2, the average thickness (in nm) is plotted on the abscissa and the sheet resistance (in ) is plotted on the ordinate in fig. 2. As can be seen from the graph in fig. 2, the average sheet resistance is inversely related to the thickness, and the larger the average thickness is, the smaller the average sheet resistance is, and the corresponding functional relation of the first metal layer 10 can be obtained by fitting the function:
R=225.14d -1.082; wherein 225.14 is used as a correction coefficient B, the range of the correction coefficient B is between 200 and 260, and the correction coefficient B accords with the functional relation: r=bd -1.082.
The measurement data of the average thickness of the first metal layer 10 and the number of magnetron sputtering times are shown in table 2.
TABLE 2
| Average thickness/nm | 20 | 28 | 69 | 141 | 173 | 192 |
| Number of sputtering times/N 2 | 2 | 4 | 8 | 16 | 20 | 24 |
Fig. 3 is a graph showing the relationship between the number of vacuum sputtering and the average thickness of the first metal layer 10, and fig. 3 is a graph showing the data in table 2, and referring to fig. 3, the abscissa in fig. 3 shows the number of sputtering N 2, and the ordinate shows the average thickness (nm). As can be seen from the fitted curve obtained from the above data, the average thickness of the first metal layer 10 is positively correlated with the number of magnetron sputtering times, and the larger the number of magnetron sputtering times is, the larger the thickness of the first metal layer 10 is, to obtain a fitted function: d= 8.2531N 2 +1.9038, where 8.2531 is a coefficient C, between the range 7.5 and 9.5, according to the above functional relation: d=cn 2 +1.9038.
In addition, according to the above relation between the average thickness of the first metal layer 10, the magnetron sputtering times and the average square resistance of the first metal layer 10, a fitting curve is obtained: relationship between average sheet resistance and number of sputtering times of first metal layer 10 made of nichrome: r= (a/) N 1 -0.99;
Wherein, the value of A is 2241.61, sigma is the conductivity of the first metal layer in the range 1700-2400, the unit is 1/(S.times.m), the conductivity of the nichrome is 105 S.times.m, the coating times N 1 is more than or equal to 1, N 1 is a positive integer, and the unit of the average square resistance R is omega.
Fig. 4 is a schematic diagram of another metal foil according to an embodiment of the present invention, and optionally, referring to fig. 4, two opposite sides of the organic film layer 20 are provided with the first metal layers 10, and the two first metal layers 10 are respectively disposed on the surface of the organic film layer 20 by any one of vacuum sputtering, evaporation plating and electroless plating.
This arrangement allows the metal foil to be used in a wider variety of applications. For example, the first metal layer 10 may be copper or aluminum, and the metal foil corresponding to the two first metal layers 10 is a composite copper foil or a composite aluminum foil, wherein the composite copper foil may be used as a negative current collector of the lithium ion battery, and the composite aluminum foil may be used as a positive current collector material of the battery.
Fig. 5 is a schematic view of another metal foil according to an embodiment of the present invention, and optionally, referring to fig. 5, the metal foil further includes a second metal layer 30, where the second metal layer 30 is disposed on a surface of the first metal layer 10 away from the organic film layer 20.
Alternatively, the thickness of the first metal layer 10 ranges from 10nm to 10 m.
Specifically, the first metal layer 10 is a seed layer of a metal conductive material, the second metal layer 30 is a plating thickening layer on the seed layer, and the design of the second metal layer 20 facilitates wider application of the metal foil, for example, as a battery anode material (current collector), a circuit board printing material, a chip packaging material, and the like.
Alternatively, the material of the second metal layer 30 is one of copper, aluminum, nickel, chromium, zinc, silver, gold, and titanium, or an alloy of at least two metals of copper, aluminum, nickel, chromium, zinc, silver, gold, and titanium.
The second metal layer 30 and the first metal layer 10 may be the same metal or different metals, corresponding to different product types.
Alternatively, the thickness of the second metal layer 30 is 0.5 m to 60 m.
When the metal foil is applied to the positive current collector or the negative current collector, the overall thickness of the metal foil can be adjusted according to the requirements of different batteries, the overall weight is greatly reduced, and the energy density of the metal foil applied to the new energy battery is improved.
Optionally, the roughness of the surface of the second metal layer 30 remote from the first metal layer 10 is 1.1 m-2.5 m.
Specifically, the roughness is evaluated by Ra or Rz, the contact surface area of the second metal layer 30 with other substances is improved by optimizing the roughness of the surface of the second metal layer, so that the binding force is increased, the surface of the metal foil and the other substances are increased, for example, when the metal foil is applied to a new energy battery, the binding force with the negative electrode active material of the battery is increased by optimizing the roughness of the surface of the second metal layer 30 far away from the first metal layer 10, the falling-off of the negative electrode active material from the surface of the PET metal foil is reduced, the reaction safety and the energy stability of the battery are improved, and the application life of the battery is prolonged.
The embodiment of the invention also provides a printed circuit board (not shown in the figure), and the metal foil according to any embodiment of the invention is adopted for circuit printing.
For example, the first metal layer 10 is a copper layer, and the first metal layer 10 is disposed on two opposite sides of the organic film layer 20, so that the metal foil is a flexible copper-clad plate, and can be used in the packaging process of the FPC.
The embodiment of the invention also provides a lithium ion battery, which comprises the metal foil according to any embodiment of the invention.
For example, the first metal layer 10 is a copper layer, the organic film layer 20 is made of PET, and the composite PET copper foil can be used as a negative electrode current collector material in a negative electrode material of a lithium ion battery.
It should be appreciated that various forms of the flows shown above may be used to reorder, add, or delete steps. For example, the steps described in the present invention may be performed in parallel, sequentially, or in a different order, so long as the desired results of the technical solution of the present invention are achieved, and the present invention is not limited herein.
The above embodiments do not limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications, combinations, sub-combinations and alternatives are possible, depending on design requirements and other factors. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the metal foil is characterized by comprising the step of preparing the metal foil, wherein the metal foil comprises a first metal layer, the first metal layer is formed by any one of vacuum sputtering, evaporation plating and chemical plating, and the plating times N 1 and the average sheet resistance R of the first metal layer meet the following relation:
R=A/*N1 -0.99
Wherein, the value range of A is 1700-2400, sigma is the conductivity of the first metal layer, the unit is 1/(, m), the coating times N 1 is more than or equal to 1, N 1 is positive integer, the unit of the average square resistance R is , and the value range of the correlation coefficient R 2 of the above relation is 0.995-0.999.
2. The method of claim 1, wherein the metal foil further comprises an organic film layer, a side of the organic film layer being in contact with the first metal layer.
3. The method of producing a metal foil according to claim 2, wherein the material of the organic film layer comprises one of PET, PP and PI.
4. The method of producing a metal foil according to claim 2, wherein the material of the organic film layer comprises PET, and the thickness of the organic film layer is 1 m to 60 m.
5. The method of claim 1, wherein the first metal layer is made of one of copper, aluminum, nickel, chromium, zinc, silver, gold, and titanium, or an alloy of at least two of copper, aluminum, nickel, chromium, zinc, silver, gold, and titanium.
6. The method of producing a metal foil according to claim 1, wherein the average thickness d of the first metal layer and the average sheet resistance R of the first metal layer satisfy the following relation:
R = B*d-1.082
wherein the unit of the average thickness d is nm, and the value range of B is 200-260.
7. The method of claim 2, wherein the first metal layer is disposed on a side surface of the organic film layer by vacuum sputtering, and the relationship between the average thickness d of the first metal layer and the number of vacuum sputtering times N 2 is:
d = C*N2+ 1.9038
Wherein the number of times of vacuum sputtering N 2 is more than or equal to 1, N 2 is a positive integer, the average thickness d is nm, and the range of C is 7.5-9.5;
preferably, the current of the vacuum sputtering is between 5 and 9A; and/or the number of the groups of groups,
The vacuum sputtering voltage is between 1000 and 1500V.
8. The method according to claim 2, wherein the first metal layers are disposed on two opposite sides of the organic film layer, and the two first metal layers are disposed on the surface of the organic film layer by any one of vacuum sputtering, evaporation plating, and electroless plating.
9. The method of producing a metal foil according to claim 2, wherein the metal foil further comprises a second metal layer provided on a surface of the first metal layer remote from the organic film layer;
Preferably, the material of the second metal layer is one of copper, aluminum, nickel, chromium, zinc, silver, gold and titanium, or an alloy containing at least two metals of copper, aluminum, nickel, chromium, zinc, silver, gold and titanium;
preferably, the thickness of the second metal layer is 0.5 m to 60 m;
the roughness of the surface of the second metal layer away from the first metal layer is 1.1-2.5 mu m.
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| CN116314844A (en) * | 2023-05-22 | 2023-06-23 | 河北海伟电子新材料科技股份有限公司 | Composite metal substrate, composite metal foil, current collector, preparation method and application |
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| CN114554685A (en) * | 2020-11-19 | 2022-05-27 | 广州方邦电子股份有限公司 | Composite metal foil and circuit board |
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