CN117497687A - Composite copper foil current collector, preparation method thereof and production system - Google Patents
Composite copper foil current collector, preparation method thereof and production system Download PDFInfo
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- CN117497687A CN117497687A CN202311479550.1A CN202311479550A CN117497687A CN 117497687 A CN117497687 A CN 117497687A CN 202311479550 A CN202311479550 A CN 202311479550A CN 117497687 A CN117497687 A CN 117497687A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000011889 copper foil Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 141
- 239000010949 copper Substances 0.000 claims abstract description 117
- 229910052802 copper Inorganic materials 0.000 claims abstract description 117
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 238000009713 electroplating Methods 0.000 claims abstract description 30
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 229920006254 polymer film Polymers 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000007747 plating Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 12
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 32
- 230000007704 transition Effects 0.000 claims description 22
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- -1 polydithio-dipropyl Polymers 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000002159 nanocrystal Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 4
- 229920002799 BoPET Polymers 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000010408 film Substances 0.000 description 23
- 230000008569 process Effects 0.000 description 15
- 238000004070 electrodeposition Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 235000007631 Cassia fistula Nutrition 0.000 description 3
- 240000004752 Laburnum anagyroides Species 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 230000006032 tissue transformation Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004804 winding 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
- H01M4/0426—Sputtering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The embodiment of the invention provides a composite copper foil current collector, a preparation method and a production system thereof, wherein the preparation method comprises the following steps: providing a substrate: the base material comprises a high polymer film and copper seed layers respectively arranged on the two side surfaces of the high polymer film, and the copper seed layers are formed in a magnetron sputtering mode; electroplating: forming a nano twin crystal copper layer on the copper seed layer in an electroplating mode to obtain a semi-finished film; the plating solution includes: copper sulfate, sulfuric acid, hydrochloric acid, additives and water; the nanometer twin crystal copper layer comprises twin crystal copper with preferred orientation of (111) crystal face and twin crystal copper with preferred orientation of (220) crystal face; and (3) heat treatment: and (3) annealing or naturally cooling the semi-finished film, wherein the heating temperature range of the annealing is not higher than 150 ℃, so that the twin crystal copper part with the preferred orientation of the (220) crystal face is converted into twin crystal copper with the preferred orientation of the (111) crystal face. The preparation process is simple, the mechanical property is excellent, and the application range of the composite copper foil current collector is wider.
Description
Technical Field
The invention relates to the technical field of conductive films, in particular to a composite copper foil current collector, a preparation method thereof and a production system thereof.
Background
The conductive metal film is a material with various good performances, and is widely applied to a battery as a positive electrode current collector or a negative electrode current collector.
The composite copper foil current collector is an indispensable material in the fields of lithium ion batteries and the like at present. In the field of electronic circuits, electrical interconnects are an important component of very large scale integrated circuits and nanoelectromechanical devices that require highly conductive, strong and stable wires. Emerging three-dimensional integrated circuit technologies also require signal transmission, power supply and heat dissipation between vertically stacked integrated circuit chips through a through-silicon via wiring system, these wires having to be deposited at high aspect ratios by dielectric-enclosed structures. In lithium ion batteries, copper foil is widely used as a current collector for anodes of lithium ion batteries, and graphite expands by about 13% when used as an anode during charge and discharge, and silicon can significantly increase in volume to 300% when used as an anode, which may cause failure of a conventional electrolytic copper foil. Therefore, to solve the above problems, it is necessary to improve the mechanical properties of the copper foil while obtaining high heat and electric conductivity properties of the copper.
In the process of implementing the present invention, the inventor finds that at least the following problems exist in the prior art: the nano goldenrain crystal copper layer structure has very good mechanical property and conductivity, and the nano goldenrain crystal copper controls the nano-scale microstructure of copper, so the nano twin crystal copper is very suitable for application in the field of composite current collectors. In the prior art, a nano twin crystal copper layer is obtained by electrochemical deposition (electroplating) after magnetron sputtering, but the nano twin crystal copper obtained by the process comprises twin crystal copper with the preferred orientation of (111) crystal faces and goldenrain crystal copper with the preferred orientation of (220) crystal faces, so that a fine crystal transition layer is formed on one side of the nano twin crystal copper layer close to a base material, and the existence of the fine crystal transition layer influences the conductivity of a composite copper foil current collector. The process difficulty of obtaining the twin crystal copper with the preferred orientation of the (111) crystal face by the magnetron sputtering process is large, so that the complete twin crystal copper with the preferred orientation of the (111) crystal face is difficult to obtain by electrochemical deposition in the subsequent process. Although some methods for eliminating the fine-grain transition layer by a heat treatment mode exist in the prior art, the coarsening of the crystal grains of the nano twin crystal copper layer can be caused while eliminating the fine-grain transition layer, so that the mechanical property of the composite copper foil current collector is reduced.
Disclosure of Invention
In view of the above, an object of the embodiments of the present invention is to provide a composite copper foil current collector, a preparation method and a production system thereof, so as to further improve the mechanical properties of the composite copper foil current collector material, and make the application range of the composite copper foil current collector material wider.
In a first aspect, an embodiment of the present invention provides a method for preparing a composite copper foil current collector, including the steps of:
providing a substrate: the base material comprises a high polymer film and copper seed layers respectively arranged on the surfaces of two sides of the high polymer film, and the copper seed layers are formed in a magnetron sputtering mode;
electroplating: forming a nano twin crystal copper layer on the copper seed layer in an electroplating mode to obtain a semi-finished film; the electroplating solution used comprises: copper sulfate, sulfuric acid, hydrochloric acid, additives and water; the nano twin crystal copper layer comprises twin crystal copper with (111) crystal face preferred orientation and twin crystal copper with (220) crystal face preferred orientation;
and (3) heat treatment: and (3) annealing or naturally cooling the semi-finished film, wherein the heating temperature range of the annealing is not higher than 150 ℃, so that the twin crystal copper part with the preferred orientation of the (220) crystal face is converted into twin crystal copper with the preferred orientation of the (111) crystal face.
Further, the polymer film comprises one of a PP film, a PET film or an AO film;
and/or the thickness of the substrate is 3.5 μm to 12 μm.
Further, the plating vacuum degree of the magnetron sputtering is less than 0.005Pa, the argon flow is 80-100ml/min, the common cooling temperature is-30-0 ℃, and the magnetron sputtering time is 90-100s.
Further, the concentration of the copper sulfate is 50-80g/L, the concentration of the sulfuric acid is 130-150g/L, and the concentration of the hydrochloric acid is 30-80mg/L; the additive comprises sodium polydithio-dipropyl sulfonate and polyethylene glycol, wherein the concentration of the sodium polydithio-dipropyl sulfonate is 12-25mg/L, the concentration of the polyethylene glycol is 180-280mg/L, and the molecular weight of the polyethylene glycol is 8000.
Further, the linear speed of the electroplating step is 3-5m/min, and the thickness of the nano twin crystal copper layer is 0.8-1.2 mu m.
Further, the electroplating step adopts a gradient current mode to carry out electroplating, the gradient current comprises a number 1 current to a number 12 current which are sequentially connected and converted, and the current density of the number 1 current is 0.15-0.35A/dm 2 The time is 20-50s; the current density of the No. 2 current is 0.35-0.45A/dm 2 The time is 20-50s; the current density of the No. 3 current is 0.45-0.55A/dm 2 The time is 20-50s; the current density of the No. 4 current is 0.55-0.65A/dm 2 The time is 20-50s; the current density of the No. 5 current is 0.55-0.95A/dm 2 The time is 40-60s; the current density of the No. 6 current is 0.95-1.15A/dm 2 The time is 40-60s; the current density of the No. 7 current is 1-1.2A/dm 2 The time is 60-80s; the current density of the No. 8 current is 1.2-1.4A/dm 2 The time is 60-80s; the current density of the No. 9 current is 1.4-1.6A/dm 2 The time is 60-80s; the current density of the No. 10 current is 1.4-1.6A/dm 2 The time is 60-80s; the current density of the No. 11 current is 1.5-1.7A/dm 2 The time is 60-100s; the current density of the No. 12 current is 1.8-2.0A/dm 2 The time is 60-100s.
Further, the annealing time is 5-10min, the conveying speed of the semi-finished film is 30m/min, and the heating temperature of the annealing is 100-150 ℃.
Further, the nano twin crystal copper layer comprises a fine crystal transition layer and a nano crystal grain layer which are formed in sequence; the fine grain transition layer is located between the copper seed layer and the nanocrystalline layer, the fine grain transition layer comprising the twin copper having a (220) crystallographic plane preferential orientation; the nanocrystalline layer includes twin copper having a preferred orientation of the (111) plane.
In a second aspect, an embodiment of the present invention provides a composite copper foil current collector manufactured by using the method for manufacturing a composite copper foil current collector as described above.
In a third aspect, an embodiment of the present invention provides a composite copper foil current collector production system, including:
the substrate production equipment is used for producing a substrate and comprises magnetron sputtering equipment, wherein the substrate comprises a high polymer film and copper seed layers respectively arranged on the surfaces of two sides of the high polymer film, and the copper seed layers are manufactured by the magnetron sputtering equipment;
electroplating equipment for forming a nano twin crystal copper layer on the copper seed layer to obtain a semi-finished film; the electroplating solution used comprises: copper sulfate, sulfuric acid, hydrochloric acid, additives and water; the nano twin crystal copper layer comprises twin crystal copper with (111) crystal face preferred orientation and twin crystal copper with (220) crystal face preferred orientation;
and the heat treatment equipment is used for annealing or naturally cooling the semi-finished film, and the heating temperature range of the annealing is not higher than 150 ℃ so as to convert the twin crystal copper part with the (220) crystal face preferred orientation into the twin crystal copper with the (111) crystal face preferred orientation.
The technical scheme has the following beneficial effects: according to the composite copper foil current collector, the preparation method and the production system thereof provided by the embodiment of the invention, the mode of preparing the nano twin crystal copper layer is very simple, the nano twin crystal copper layer with larger internal stress is generated by adopting a special electroplating solution, and then the twin crystal copper part with the preferred orientation of the (220) crystal face of the nano twin crystal copper layer is converted into the twin crystal copper with the preferred orientation of the (111) crystal face by a subsequent heat treatment process, so that a fine crystal transition layer is eliminated, and the electric conduction and mechanical properties of the composite copper foil current collector are improved. The heat treatment of the scheme adopts a natural cooling or low-temperature annealing process, reduces the coarsening of the crystal grains on the basis of realizing the transformation of the crystal grain structure, and further improves the mechanical property.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a method for preparing a composite copper foil current collector according to an embodiment of the invention.
Fig. 2 is a graph showing the comparison of the X-ray diffraction detection results of the nano twin crystal copper layer before and after baking in the embodiment of the present invention.
Detailed Description
Features and exemplary embodiments of various aspects of the invention are described in detail below. In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without some of these specific details. The following description of the embodiments is merely intended to provide a better understanding of the invention by showing examples of the invention. In the drawings and the following description, at least some well-known structures and techniques have not been shown in detail in order not to unnecessarily obscure the present invention; also, the dimensions of some of the structures may be exaggerated for clarity. Furthermore, the described features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
As shown in fig. 1, the preparation method of the composite copper foil current collector according to the embodiment of the invention comprises the following steps:
s1, providing a substrate: the base material comprises a high polymer film and copper seed layers respectively arranged on the two side surfaces of the high polymer film, wherein the copper seed layers are formed in a magnetron sputtering mode, and the copper seed layers on the two side surfaces of the high polymer film can be formed simultaneously or can be formed on one side and then the other side.
S1.1, providing a PP film (polypropylene film), a PET film (polyester film) or an AO film (namely, a film formed by evaporating a layer of alumina on a high polymer substrate). The thickness of the polymer film is in the range of 3.5 μm to 12. Mu.m.
S1.2, forming copper seed layers on two sides of the polymer film respectively through magnetron sputtering. The vacuum degree of magnetron sputtering is less than 0.005Pa, the argon flow is 80-100ml/min, the common cooling temperature (the cooling temperature of a main roller during the operation of magnetron sputtering) is-30-0 ℃, the magnetron sputtering time is 90-100s, the winding speed is 4-5m/min, the copper target power is 13KW, and the coating voltage is 600+ -20V. Preferably, the normal cooling temperature is-10 ℃.
S2, electroplating (electrodeposition) step: and respectively forming nano twin crystal copper layers on the copper seed layers in an electroplating mode to obtain a semi-finished film.
The linear speed of electroplating is 3-5m/min, and the thickness of the nano twin crystal copper layer is 0.8-1.2 mu m, preferably 1 mu m.
The electroplating solution used comprises: copper sulfate, sulfuric acid, hydrochloric acid, additives and water. The concentration of the copper sulfate is 50-80g/L, the concentration of the sulfuric acid is 130-150g/L, and the concentration of the hydrochloric acid is 30-80mg/L. The additive comprises sodium polydithio-dipropyl sulfonate and polyethylene glycol, wherein the concentration of the sodium polydithio-dipropyl sulfonate is 12-25mg/L, the concentration of the polyethylene glycol is 180-280mg/L, and the molecular weight of the polyethylene glycol is 8000.
The electroplating step adopts a gradient current mode to carry out electroplating, wherein the gradient current comprises a number 1 current to a number 12 current which are sequentially connected and converted, and the current density of the number 1 current is 0.15-0.35A/dm 2 (the current is 10-20A) for 20-50s; the current density of the No. 2 current is 0.35-0.45A/dm 2 (the current is 20-30A) for 20-50s; the current density of the No. 3 current is 0.45-0.55A/dm 2 (current magnitude is 30-40A) for 20-50s; the current density of the No. 4 current is 0.55-0.65A/dm 2 (current magnitude is 40-50A) for 20-50s; the current density of the No. 5 current is 0.55-0.95A/dm 2 (current is 60-80A) for 40-60s; the current density of the No. 6 current is 0.95-1.15A/dm 2 (current is 80-100A) for 40-60s; the current density of the No. 7 current is 1-1.2A/dm 2 (the current is 100-120A) for 60-80s; the current density of the No. 8 current is 1.2-1.4A/dm 2 (current is 120-140A) for 60-80s; the current density of the No. 9 current is 1.4-1.6A/dm 2 (current magnitude is 160-190A) for 60-80s; the current density of the No. 10 current is 1.4-1.6A/dm 2 (current is 190-220A) for 60-80s; the electricity of the No. 11 currentThe flow density is 1.5-1.7A/dm 2 (current magnitude is 230-270A) for 60-100s; the current density of the No. 12 current is 1.8-2.0A/dm 2 (current magnitude 280-320A) for 60-100s.
The nano twin crystal copper layer comprises twin crystal copper with (111) crystal face preferred orientation and twin crystal copper with (220) crystal face preferred orientation. The nano twin crystal copper layer comprises a fine crystal transition layer and a nano crystal grain layer which are formed in sequence. The fine crystal transition layer is positioned between the copper seed layer and the nano crystal grain layer, and is mainly twin crystal copper with (220) crystal face preferred orientation; the nanocrystalline layer is mainly twin crystal copper with (111) crystal face preferred orientation.
S3, heat treatment: and (3) annealing (baking) or naturally cooling the semi-finished film, wherein the heating temperature range of the annealing is not higher than 150 ℃ so as to convert the twin crystal copper part with the (220) crystal face preferred orientation into the twin crystal copper with the (111) crystal face preferred orientation.
The annealing time is 5-10min, the conveying speed of the semi-finished film is 30m/min, and the heating temperature of the annealing is 100-150 ℃, preferably 150 ℃.
The embodiment of the invention also provides a copper foil current collector production system, which comprises:
the substrate production equipment is used for producing a substrate and comprises magnetron sputtering equipment, wherein the substrate comprises a high polymer film and copper seed layers respectively arranged on the surfaces of two sides of the high polymer film, and the copper seed layers are manufactured by the magnetron sputtering equipment;
electroplating equipment for forming a nano twin crystal copper layer on the copper seed layer to obtain a semi-finished film; the electroplating solution used comprises: copper sulfate, sulfuric acid, hydrochloric acid, additives and water; the nano twin crystal copper layer comprises twin crystal copper with (111) crystal face preferred orientation and twin crystal copper with (220) crystal face preferred orientation;
and the heat treatment equipment is used for annealing or naturally cooling the semi-finished film, and the heating temperature range of the annealing is not higher than 150 ℃ so as to convert the twin crystal copper part with the preferred orientation of the (220) crystal face into the twin crystal copper with the preferred orientation of the (111) crystal face.
It is found that the prepared copper layer has stress when forming a twin structure and is driven by the stress to change the twin structure after forming the twin structure. The copper layer is driven by stress in a natural state to be converted into a nano twin structure of (111) from a nano twin structure of (220), the conversion can be accelerated by low-temperature baking, the production efficiency is improved, meanwhile, coarse structure crystals cannot be caused, and the heat treatment is more energy-saving and takes longer time if a natural cooling mode is adopted.
In the electrochemical deposition preparation process of the nano twin crystal copper layer, a fine crystal transition layer always exists between the substrate material and the nano crystal grain layer due to inconsistent structure or crystal orientation of the substrate material and the nano twin crystal copper. Many factors influence the thickness of the fine-grain transition layer, including the degree of mismatch of the copper seed layer and nano twin copper, the formulation of the electroplating bath for electrodeposition, the setting of electroplating process parameters, and the like, are closely related, and the thickness of the fine-grain transition layer is about a fraction of a micron.
It has been reported by researchers that if a strictly (111) preferentially oriented copper seed layer is used, i.e., the degree of lattice mismatch between the seed layer and the nano-twin copper structure is very small, the fine transition layer can be eliminated and the nano-twin copper structure having the twin plane (111) can be epitaxially grown directly on the (111) copper seed layer. However, there is a difficulty in producing a copper seed layer of a specific orientation by magnetron sputtering, and thus it is not easy to want to obtain a copper thin film material of full nano twin copper structure from bottom to top. And only a substrate of a specific material with a specific crystal orientation can be used, which greatly restricts the application of the nano twin crystal copper film. Furthermore, in certain specific applications, such as applications requiring ultra-high conductivity, inclusion of a fine grain transition layer in the nano-twin copper coating can adversely affect its conductivity. In thin film applications of a few microns, the fine grain transition layer is also not negligible because the overall plating thickness is on the same order of magnitude as the fine grain transition layer thickness. Aiming at the problem, the solution proposed by the embodiment of the invention is as follows: firstly, electrodepositing is adopted to prepare nano twin crystal copper tissues with very large internal stress, and then the obtained coating is subjected to heat treatment. Because nano twin crystal copper structure is a special texture generated by intermittent release of plating growth stress in the electrodeposition process, electrodeposition conditions are often severe, and the electrodeposited plating layer still has larger growth stress. According to the embodiment of the invention, the growth stress of the nano twin crystal structure is further increased by selecting a severe deposition condition (a specific plating solution formula is used, namely a copper sulfate plating solution system, a lower concentration of main salt, a lower concentration of acid, a specific additive and the like and technological parameters are used), so that the prepared plating layer has larger internal stress, and a fine crystal transition layer with the thickness of 0.1-20 mu m exists between the nano crystal grain layer and the substrate material. And in the subsequent heat treatment process, the growth stress is utilized to convert the structure of the fine-grain transition layer into a nano twin structure. Unlike the common heat treatment method, the copper plating layer with lower stress generally releases the plating layer stress in the heat treatment process, and the plating layer crystal grains can be coarsened in size, but no new nanometer twin crystal structure is generated.
The preparation method of the embodiment of the invention is different from a method for preparing a plating layer of a full-nanometer twin crystal copper structure from bottom to top by direct electrodeposition, and is different from a method for limiting a special matrix material and crystal orientation thereof, and is a brand new preparation method for preparing the full-nanometer twin crystal copper structure by utilizing a special electrodeposition preparation method and matching with a special heat treatment method. The growth stress of the plating layer is further released in the heat treatment process, so that the obtained plating layer (nano twin crystal copper layer) has small stress and higher heat stability than a nano twin crystal copper film generated by direct electrodeposition. It should be noted, however, that the heat treatment conditions differ depending on the electrodeposition conditions. But cannot be heat treated at too high a temperature and time, otherwise grain coarsening may occur in the original nano twin copper structure.
Fig. 2 is a graph showing the comparison of the results of X-ray diffraction detection of a nano twin copper layer before and after baking, wherein the ordinate represents the intensity after diffraction (intensity a.u.), and the abscissa represents twice the incident angle of X-rays. The left graph in fig. 2 shows the X-ray diffraction detection result of the nano twin copper layer before baking, and the right graph in fig. 2 shows the X-ray diffraction detection result of the nano twin copper layer after baking. As can be seen from fig. 2, after heat treatment, the duty ratio of the twin crystal copper with the preferred orientation of the (111) crystal face is effectively improved, so that the twin crystal copper with the preferred orientation of the (220) crystal face is mostly converted into the twin crystal copper with the preferred orientation of the (111) crystal face, but the duty ratio of the twin crystal copper with the preferred orientation of the (200) crystal face is basically unchanged, and no obvious tissue transformation occurs.
The composite copper foil current collector prepared by the preparation method provided by the embodiment of the invention has the advantages of small stress, high thermal stability and the like. The preparation method related to the embodiment of the invention is widely applicable to common substrate materials in various microelectronics industries, and further expands the application range of nano twin crystal copper film materials. According to the preparation method, the nano twin crystal copper film with different microstructures can be obtained by adjusting the content of main salt, the content of acid, chloride ions and additives in the plating solution, and the electrodeposition process parameters and the heat treatment process parameters, the corresponding twin crystal sheet layer spacing can be adjusted within a certain range, the controllable adjustment of the film material performance can be realized, and the application range of the material is enlarged. The electrodeposition and heat treatment process related by the preparation method disclosed by the invention is simple to operate, and has the beneficial effects of easiness in popularization and cost saving.
In the description of the present invention, it should be noted that the orientation or positional relationship indicated by "upper, lower, inner and outer", etc. in terms are based on the orientation or positional relationship shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the apparatus or element in question must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first, second, or third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The terms "mounted, connected, and coupled" should be construed broadly in this disclosure unless otherwise specifically indicated and defined, such as: can be fixed connection, detachable connection or integral connection; it may also be a mechanical connection, an electrical connection, or a direct connection, or may be indirectly connected through an intermediate medium, or may be a communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
While the invention has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present invention is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (10)
1. The preparation method of the composite copper foil current collector is characterized by comprising the following steps of:
providing a substrate: the base material comprises a high polymer film and copper seed layers respectively arranged on the surfaces of two sides of the high polymer film, and the copper seed layers are formed in a magnetron sputtering mode;
electroplating: forming a nano twin crystal copper layer on the copper seed layer in an electroplating mode to obtain a semi-finished film; the electroplating solution used comprises: copper sulfate, sulfuric acid, hydrochloric acid, additives and water; the nano twin crystal copper layer comprises twin crystal copper with (111) crystal face preferred orientation and twin crystal copper with (220) crystal face preferred orientation;
and (3) heat treatment: and (3) annealing or naturally cooling the semi-finished film, wherein the heating temperature range of the annealing is not higher than 150 ℃, so that the twin crystal copper part with the preferred orientation of the (220) crystal face is converted into twin crystal copper with the preferred orientation of the (111) crystal face.
2. The method for preparing a composite copper foil current collector according to claim 1, wherein the polymer film comprises one of PP film, PET film or AO film;
and/or the thickness of the substrate is 3.5 μm to 12 μm.
3. The method for preparing a composite copper foil current collector according to claim 1 or 2, wherein the plating vacuum degree of the magnetron sputtering is less than 0.005Pa, the argon flow is 80-100ml/min, the common cooling temperature is-30 ℃ -0 ℃, and the magnetron sputtering time is 90-100s.
4. The method for preparing a composite copper foil current collector according to claim 3, wherein the concentration of copper sulfate is 50-80g/L, the concentration of sulfuric acid is 130-150g/L, and the concentration of hydrochloric acid is 30-80mg/L; the additive comprises sodium polydithio-dipropyl sulfonate and polyethylene glycol, wherein the concentration of the sodium polydithio-dipropyl sulfonate is 12-25mg/L, the concentration of the polyethylene glycol is 180-280mg/L, and the molecular weight of the polyethylene glycol is 8000.
5. The method for preparing a composite copper foil current collector according to any one of claims 1, 2 or 4, wherein the linear speed of the electroplating step is 3-5m/min, and the thickness of the nano twin crystal copper layer is 0.8-1.2 μm.
6. The method for preparing a composite copper foil current collector according to any one of claims 1, 2 or 4, wherein the electroplating step adopts a gradient current mode for electroplating, the gradient current comprises a number 1 current to a number 12 current which are sequentially connected and converted, and the current density of the number 1 current is 0.15-0.35A/dm 2 The time is 20-50s; the current density of the No. 2 current is 0.35-0.45A/dm 2 The time is 20-50s; the current density of the No. 3 current is 0.45-0.55A/dm 2 The time is 20-50s; the current density of the No. 4 current is 0.55-0.65A/dm 2 The time is 20-50s; the current density of the No. 5 current is 0.55-0.95A/dm 2 The time is 40-60s; the current density of the No. 6 current is 0.95-1.15A/dm 2 The time is 40-60s; the current density of the No. 7 current is 1-1.2A/dm 2 The time is 60-80s; the current density of the No. 8 current is 1.2-1.4A/dm 2 The time is 60-80s; the current density of the No. 9 current is 1.4-1.6A/dm 2 The time is 60-80s; the current density of the No. 10 current is 1.4-1.6A/dm 2 The time is 60-80s; the current density of the No. 11 current is 1.5-1.7A/dm 2 The time is 60-100s; the current density of the No. 12 current is 1.8-2.0A/dm 2 The time is 60-100s.
7. The method for preparing a composite copper foil current collector according to any one of claims 1, 2 or 4, wherein the annealing time is 5 to 10min, the transport speed of the semi-finished film is 30m/min, and the heating temperature of the annealing is 100 to 150 ℃.
8. The method for preparing a composite copper foil current collector according to any one of claims 1, 2 or 4, wherein the nano twin copper layer comprises a fine crystal transition layer and a nano crystal grain layer formed in sequence; the fine grain transition layer is located between the copper seed layer and the nanocrystalline layer, the fine grain transition layer comprising the twin copper having a (220) crystallographic plane preferential orientation; the nanocrystalline layer includes twin copper having a preferred orientation of the (111) plane.
9. A composite copper foil current collector manufactured by the method for manufacturing a composite copper foil current collector according to any one of claims 1 to 8.
10. A composite copper foil current collector production system, comprising:
the substrate production equipment is used for producing a substrate and comprises magnetron sputtering equipment, wherein the substrate comprises a high polymer film and copper seed layers respectively arranged on the surfaces of two sides of the high polymer film, and the copper seed layers are manufactured by the magnetron sputtering equipment;
electroplating equipment for forming a nano twin crystal copper layer on the copper seed layer to obtain a semi-finished film; the electroplating solution used comprises: copper sulfate, sulfuric acid, hydrochloric acid, additives and water; the nano twin crystal copper layer comprises twin crystal copper with (111) crystal face preferred orientation and twin crystal copper with (220) crystal face preferred orientation;
and the heat treatment equipment is used for annealing or naturally cooling the semi-finished film, and the heating temperature range of the annealing is not higher than 150 ℃ so as to convert the twin crystal copper part with the (220) crystal face preferred orientation into the twin crystal copper with the (111) crystal face preferred orientation.
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| CN117913286A (en) * | 2024-03-15 | 2024-04-19 | 江阴纳力新材料科技有限公司 | Composite copper-based current collector, preparation method thereof and lithium ion battery |
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| CN117913286A (en) * | 2024-03-15 | 2024-04-19 | 江阴纳力新材料科技有限公司 | Composite copper-based current collector, preparation method thereof and lithium ion battery |
| CN117913286B (en) * | 2024-03-15 | 2024-05-17 | 江阴纳力新材料科技有限公司 | Composite copper-based current collector, preparation method thereof and lithium ion battery |
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