WO2024051475A1 - Composite current collector manufacturing method and manufacturing device - Google Patents
Composite current collector manufacturing method and manufacturing device Download PDFInfo
- Publication number
- WO2024051475A1 WO2024051475A1 PCT/CN2023/113801 CN2023113801W WO2024051475A1 WO 2024051475 A1 WO2024051475 A1 WO 2024051475A1 CN 2023113801 W CN2023113801 W CN 2023113801W WO 2024051475 A1 WO2024051475 A1 WO 2024051475A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- base material
- current collector
- composite current
- material strip
- strip
- Prior art date
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 108
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 186
- 229910052751 metal Inorganic materials 0.000 claims abstract description 130
- 239000002184 metal Substances 0.000 claims abstract description 130
- 238000000034 method Methods 0.000 claims abstract description 40
- 230000007246 mechanism Effects 0.000 claims description 102
- 238000002360 preparation method Methods 0.000 claims description 67
- 238000007772 electroless plating Methods 0.000 claims description 62
- 238000007788 roughening Methods 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 39
- 238000007747 plating Methods 0.000 claims description 38
- 230000004913 activation Effects 0.000 claims description 36
- 238000009713 electroplating Methods 0.000 claims description 30
- 238000000576 coating method Methods 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 27
- 230000001235 sensitizing effect Effects 0.000 claims description 21
- 238000004804 winding Methods 0.000 claims description 11
- 230000003213 activating effect Effects 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 238000009966 trimming Methods 0.000 claims description 9
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- 239000010949 copper Substances 0.000 description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- 229910052802 copper Inorganic materials 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 16
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- 238000004140 cleaning Methods 0.000 description 16
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- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000007756 gravure coating Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
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- 238000010329 laser etching Methods 0.000 description 2
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- 229920001155 polypropylene Polymers 0.000 description 2
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- 238000005507 spraying Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 241000283070 Equus zebra Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 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 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000005250 beta ray Effects 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer 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
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000037303 wrinkles Effects 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- 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
-
- 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
-
- 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
- H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
Definitions
- the present disclosure relates to a composite current collector preparation method and preparation device.
- vacuum physical vapor deposition is accompanied by high temperatures, and the substrate is prone to problems such as deformation, wrinkles, bubbles, perforations, and brittleness in high-temperature environments.
- the substrate is very light and thin, and the impact of high-energy particles during vacuum sputtering, corrosion during electroless plating, and edge current effects during electroplating can easily cause perforation and damage to the substrate.
- the substrate needs to withstand the tension of the tape, damage to the edges of the substrate can easily lead to tape breakage. Therefore, existing methods lead to low yields when preparing composite current collectors.
- a composite current collector preparation method including the steps:
- An active area is formed in the middle of the surface of the base material strip, and a blank area is formed on both sides of the base material strip along the width direction.
- the active area and the blank area are both strip-shaped and extend along the The lengthwise extension of the strip of base material;
- edge portions or the blank areas on both sides of the metal layer along the width direction are cut off to prepare a composite current collector.
- the step of forming an active area in the middle of the surface of the base material strip and forming a blank area on both sides of the base material strip along the width direction includes:
- the areas on both sides of the base material strip along the width direction that have not been roughened and have not been coated with the sensitizing activating liquid form the blank area.
- the step of roughening the middle part of the surface of the base material strip includes: roughening a plurality of strip-shaped areas on the surface of the base material strip, the strip-shaped areas being located on the surface of the base material strip.
- the middle part of the surface of the base material strip and arranged at intervals along the width direction of the base material strip;
- the strip-shaped area after roughening treatment is coated with a sensitizing activation liquid to form the active area, and the area between the adjacent strip-shaped areas is not roughened and is not coated with the sensitizing activation liquid. Create the blank area.
- the composite current collector includes a negative electrode composite current collector
- the step of forming a metal layer in the active region includes:
- Electroless plating is performed on the base material strip to form a metal film attached to the active area;
- the electroless plated base material strip is electroplated to form a predetermined surface on the surface of the metal film. thickness of the metal layer.
- the base material strip is electroplated using brush plating.
- the composite current collector includes a positive electrode composite current collector
- the step of forming a metal layer in the active area includes: electroless plating the base material strip to form a predetermined thickness in the active area. of the metal layer.
- the step further includes: forming an anti-oxidation layer on a surface of the metal layer facing away from the base material strip.
- the base material tape is unwound in a continuous tape conveying manner; and the prepared composite current collector is wound up in a continuous tape conveying manner.
- a composite current collector preparation device including:
- Unwinding mechanism for supplying strips of base material
- a pretreatment mechanism is used to form an active area in the middle of the surface of the base material strip, and to form a blank area on both sides of the base material strip along the width direction.
- the active area and the blank area are both in the shape of Strip shape and extending along the length direction of the base material strip;
- An edge cutting mechanism is used to cut off the edge portions or the blank areas on both sides of the metal layer along the width direction to prepare a composite current collector.
- the unwinding mechanism can continuously unwind the base material strip
- the composite current collector preparation device further includes a rewinding mechanism, and the rewinding mechanism can continuously rewind the composite current collector.
- the above-mentioned composite current collector preparation method and preparation device form an active area in the middle of the surface of the base material strip through selective pretreatment, and form a blank area on both sides of the base material strip along the width direction.
- the blank area is unprocessed area, so the edges on both sides of the base material strip will not be damaged.
- in shape In the process of forming a metal layer, the operation is only performed on the active area, and no metal layer is formed on the blank area.
- damage such as perforations to the base material strip often appears at the edge of the metal layer. It can be seen that the damage to the edge of the base material strip can be minimized during the preparation process, thereby maintaining a high mechanical strength of the base material strip. Moreover, damage at the edge of the metal layer can be subsequently removed. Therefore, the above composite current collector preparation method can significantly improve the yield rate.
- Figure 1 is a schematic structural diagram of a composite current collector prepared in an embodiment of the present disclosure
- Figure 2 is a schematic flow chart of a composite current collector preparation method in one embodiment of the present disclosure
- FIG 3 is a schematic diagram of the processing scene corresponding to the composite current collector preparation method shown in Figure 2;
- Figure 4 is a detailed schematic diagram of scene (d) to scene (e) shown in Figure 3;
- Figure 5 is a module schematic diagram of a composite current collector preparation device in one embodiment of the present disclosure.
- Figure 6 is a schematic structural diagram of the unwinding mechanism in the composite current collector preparation device shown in Figure 5;
- Figure 7 is a schematic structural diagram of the roughening treatment mechanism in the composite current collector preparation device shown in Figure 5;
- Figure 8 is a schematic structural diagram of a roughening processing mechanism in another embodiment
- Figure 9 is a schematic structural diagram of the activation treatment mechanism in the composite current collector preparation device shown in Figure 5;
- Figure 10 is a schematic structural diagram of the electroless plating mechanism in the composite current collector preparation device shown in Figure 5;
- FIG 11 is a schematic structural diagram of the electroplating mechanism in the composite current collector preparation device shown in Figure 5;
- Figure 12 is a module schematic diagram of a composite current collector preparation device in another embodiment
- Figure 13 is a top view of a composite current collector produced in another embodiment
- FIG. 14 is a schematic cross-sectional view of the composite current collector shown in FIG. 13 .
- first and second are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as “first” and “second” may explicitly or implicitly include at least one of these features.
- “plurality” means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.
- connection In this disclosure, unless otherwise explicitly stated and limited, the terms “installation”, “connection”, “connection”, “fixing” and other terms should be understood in a broad sense. For example, it can be a fixed connection or a detachable connection. , or integrated; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be an internal connection between two elements or an interactive relationship between two elements, unless otherwise specified limitations. For those of ordinary skill in the art, the specific meanings of the above terms in this disclosure can be understood according to specific circumstances.
- a first feature is “on” or “on” a second feature.
- “Lower” may mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediary.
- the terms “above”, “above” and “above” the first feature is above the second feature may mean that the first feature is directly above or diagonally above the second feature, or simply means that the first feature is higher in level than the second feature.
- “Below”, “below” and “beneath” the first feature to the second feature may mean that the first feature is directly below or diagonally below the second feature, or simply means that the first feature has a smaller horizontal height than the second feature.
- the present disclosure provides a composite current collector preparation method, which is used to prepare the composite current collector 200 as shown in FIG. 1 .
- the composite current collector 200 includes a base material strip 210 and metal layers 220 located on two opposite surfaces of the base material strip 210 .
- the base material tape 210 is an insulating material, and may be any polymer material such as polyethylene terephthalate, polypropylene, polyamide, polyimide, polyvinyl chloride, and polystyrene.
- the base material strip 210 is in the shape of a film and plays a supporting role, and its thickness is generally between 2 ⁇ m and 12 ⁇ m.
- the metal layer 220 plays a conductive role, and its thickness is generally between 700nm and 2000nm.
- the composite current collector 200 can be used as either a positive electrode or a negative electrode of a lithium battery. The difference is that the materials of the metal layer 220 are different.
- the material of the metal layer 220 is generally copper or copper alloy.
- the metal layer 220 may also be a multi-layer composite structure in which the mass ratio of copper is not less than 80%.
- the material of the metal layer 220 is generally aluminum or aluminum alloy.
- the metal layer 220 can also be a multi-layer composite structure with a mass ratio of aluminum of not less than 80%.
- the composite current collector preparation method in one embodiment of the present disclosure includes steps S110 to S140.
- Step S110 providing a base material tape 210.
- the base material tape 210 is generally unrolled in the form of a material tape, and can be prepared in advance and stored on the unwinding reel.
- the provided base material tape 210 runs along a preset direction, the tape running direction is the length direction of the base material tape 210 , and the direction perpendicular to the length direction is the width direction of the base material tape 210 .
- This step corresponds to scenario (a) shown in Figure 3.
- Step S120 Form an active area 201 in the middle of the surface of the base material strip 210, and form a blank area 202 on both sides of the surface width direction of the base material strip 210.
- the active area 201 and the blank area 202 are in a strip shape and extend along the base material.
- the strip 210 extends lengthwise.
- the surface of the base material strip 210 needs to be pre-treated before coating to obtain the active area 201.
- the purpose of the pre-treatment is to enhance the adhesion ability of the surface of the base material strip 210 to the metal material. This step corresponds to scenario (b) shown in Figure 3.
- the entire surface of the base material strip 210 is not processed during pretreatment. Specifically, the pretreatment only targets the middle area of the surface of the base material strip 210.
- the treated area is the active area 201, and the adhesion ability to metal materials is improved.
- no preprocessing is performed on both sides of the surface width direction of the base material strip 210, thereby forming a blank area 202.
- the middle area refers to the area between the blank areas 202 on both sides of the base material strip 210 .
- Both the active area 201 and the blank area 202 extend along the length of the base material strip 210 .
- the active area 201 is integrated and located in the middle area of the base material strip 210, while the blank areas 202 are only distributed on both sides of the base material strip 210.
- the resulting composite current collector 200 is as shown in Figure 3 (e ) shown in the order bar structure.
- a plurality of active areas 201 spaced along the width direction of the base material band 210 may also be formed on the surface of the base material band 210 , except for the blank areas distributed on both sides of the base material band 210 in the width direction. 202, a blank area 202 is also formed between two adjacent active areas 201. Therefore, the prepared composite current collector 200 has multiple structures similar to zebra stripes as shown in FIGS. 13 and 14 .
- the above-mentioned step 120 includes: roughening the middle part of the surface of the base material strip 210; and applying a sensitizing activation liquid to the roughened area of the surface of the base material strip 210 to form the active area 201.
- the method of roughening treatment may be physical roughening, chemical roughening, or a combination of physical roughening and chemical roughening.
- Specific methods of physical roughening include laser etching, ultraviolet irradiation, plasma irradiation and corona treatment on preset areas.
- the specific method of chemical roughening includes soaking the preset area with one or more aqueous solutions containing hydrogen peroxide, sulfuric acid, chromic acid, and potassium permanganate.
- cleaning and drying can be carried out depending on the specific situation.
- the sensitizing activation liquid can be applied to the roughened area through precision coating.
- the sensitization activation liquid may be an aqueous solution containing one or more ions or colloids among copper, tin, silver, platinum, palladium, and manganese.
- the base material belt 210 After activating the middle part of the surface of the base material belt 210, the base material belt 210 may also be cleaned and dried as appropriate.
- the above step 120 includes: aligning a plurality of strips on the surface of the base material strip 210 The area is roughened, and the strip-shaped area is located in the middle of the surface of the base material strip 210 and is spaced apart along the width direction of the base material strip 210 .
- the sensitizing activating liquid is applied to the roughened strip area to form the active area 201, and the base material strip 210 between adjacent strip areas is not roughened and is not coated with the sensitizing activating liquid.
- a blank area 202 is formed.
- the blank areas 202 are also formed between two adjacent active areas 201.
- step S130 a metal layer 220 is formed in the active area 201.
- the metal layer 220 can be formed on the active area 201 on the surface of the base material strip 210 through various coating methods such as physical vapor deposition, chemical vapor deposition, electroless plating, and electroplating.
- the above-mentioned step S130 includes: performing electroless plating on the base material strip 210 to form a metal film 221 attached to the active area 201.
- This step corresponds to the scene (c) shown in Figure 3;
- the base material strip 210 is electroplated to form a metal layer 220 with a predetermined thickness on the surface of the metal film 221.
- This step corresponds to scene (d) shown in FIG. 3 .
- the produced metal layer 220 is a copper layer, a copper alloy layer or a multi-layer composite structure containing copper.
- the base material strip 210 can be immersed in a metal electroless plating solution one or more times.
- the metal electroless plating solution can be a copper plating solution, a nickel plating solution or a copper-nickel alloy plating solution.
- the metal film 221 that can be formed after electroless plating can be a nickel plating layer, a copper plating layer, a copper-nickel alloy layer, or a combination thereof.
- the thickness of the metal film 221 is much smaller than the thickness of the metal layer 220, generally between 20nm and 400nm.
- the sheet resistance of the metal film 221 can be 200m ⁇ /square to 1000m ⁇ /square.
- the metal film 221 After electroless plating and before electroplating, the metal film 221 generally needs to be cleaned and dried. In addition, the metal film 221 can also be acidified when necessary.
- the function of electroplating is to continue to deposit metal materials on the surface of the metal film 221, thereby gradually thickening the metal film 221 until a metal layer 220 with a required thickness is obtained.
- the thickness of the metal layer 200 may be 700 nm to 2000 nm.
- the sheet resistance of the metal layer 200 is 1 m ⁇ /square to 180 m ⁇ /square, and has good electrical conductivity.
- Electroless plating can smoothly form a thin metal film 221 on the surface of the non-metallic base material strip 210, thereby providing a basis for the subsequent formation of the metal layer 220.
- the environment of electroless plating is relatively mild, and the impact on the surface of the base material strip 210 is smaller.
- the electroplating process is more efficient when forming the metal layer 220, and the formed metal layer 220 is denser and has better conductivity. Therefore, the above method can combine the advantages of both electroless plating and electroplating processes.
- the base material strip 210 is electroplated using brush plating. Since brush plating does not require a plating tank, the equipment is simple, the floor space is small, and the cost is low. Moreover, when brush plating is used, the non-coating area, that is, the blank area 202, does not need to be covered with protective material, so the operation process can be simplified, thereby improving the preparation efficiency.
- an adhesive layer can also be formed in the activation area 201.
- This adhesive layer serves as a transition and can form a strong bond with both polymer and metal materials. Binding force.
- the adhesive layer may include a polyurethane adhesive.
- the metal layer 220 is only formed in the active area 201 , that is, in the middle of the base material strip 210 , the metal layer 220 is not formed in the blank area 202 . Therefore, the perforation or damage caused by the edge current effect during electroplating will be mainly concentrated in the middle of the base material strip 210 corresponding to the edge of the metal layer 220 , while the edge of the base material strip 210 will maintain good integrity. Defects in the middle of the base material tape 210 have less impact on the mechanical strength of the base material tape 210 than defects at the edges, so the base material tape 210 is less likely to be damaged or broken during the tape transport process.
- the base material strip 210 since the base material strip 210 has undamaged edges, it can withstand greater tension. Therefore, on the premise of ensuring continuous belting, the belt conveying speed of the base material belt 210 can be increased, thereby further improving the preparation efficiency of the composite current collector 200 .
- Step S140 cut off the edge portions or blank areas 202 on both sides of the metal layer 220 along the width direction to prepare the composite current collector 200 .
- the blank area 202 does not have electrical conductivity, it cannot be used as an electrode and needs to be removed before preparing the electrode. During the cutting operation, only the portion of the base material strip 210 corresponding to the blank area 202 may be cut off, or part of the metal layer 220 may be cut off while cutting off the blank area 202 .
- the trimming component 341 cuts along the dotted line in the figure, so the width of the cutout is greater than the width of the blank area 202, so that The edge portions on both sides of the metal layer 220 along the width direction are cut off. In this way, during the process of cutting off the blank area 202 , the damage at the edge of the metal layer 220 can be cut away, so that a composite current collector 200 with better quality can be obtained, and the yield rate of the composite current collector 200 can be significantly improved.
- a step is further included: forming an anti-oxidation layer on the surface of the metal layer 220.
- the anti-oxidation layer may be a passivation layer formed on the metal layer 220 after passivation treatment, so that the metal layer 220 has better anti-oxidation performance.
- the composite current collector 200 can be put into a chemical passivation pool, and the surface of the metal layer 220 can be passivated with a solution containing chromium or nickel.
- the base material tape 210 is unrolled in a continuous tape conveying manner, and the prepared composite current collector 200 is rolled up in a continuous tape conveying manner.
- the above method can realize the continuous preparation of 200 roll-to-roll composite current collectors, which helps to improve efficiency.
- the rolled composite current collector 200 can be stored in the form of a roll and can be directly unrolled when used. Obviously, in other embodiments, the winding step can be omitted, and the prepared composite current collector 200 can directly enter the next process such as coating or slicing to prepare lithium battery electrodes.
- PET tape polyethylene terephthalate with a thickness of 6 ⁇ m and a width of 1750mm, that is, PET tape.
- the running speed of the PET tape is about 40m/min;
- corona treatment to roughen the area within the width of 1300mm in the middle of the PET tape.
- the corona power is roughly 360W to 1200W.
- inkjet printing to roughen the area within the width of 1300mm in the middle of the PET tape.
- the roughened area is coated with a sensitizing activation liquid, which is an aqueous solution containing 1g/L to 2g/L AgNO 3 . After the sensitization activation liquid is coated, the surface is activated through double-sided ultraviolet irradiation, so that the area within the width of 1300mm in the middle of the PET strip can become the active area 201;
- the electroless plating temperature is generally controlled between 35°C and 53°C.
- the metal electroless plating solution contains 10g/L to 15g/L copper sulfate and potassium tartrate.
- a copper-containing metal film 221 is obtained in the active area 201 of the PET strip;
- the electroless plated PET strip is electroplated with copper, and the metal film 221 is thickened until the thickness reaches 700 nm to 2000 nm.
- the plating solution for brush copper plating is an aqueous solution containing 150g/L to 250g/L of copper sulfate, 50g/L to 70g/L of sulfuric acid and a small amount of other additives.
- the tape traveling speed of PET tape is 30m/min ⁇ 50m/min, so it is necessary to set up a tension control mechanism for buffering and release so that the tape traveling in each process can match;
- the obtained metal layer 220 is first cleaned with deionized water, then immersed in an aqueous solution containing chromate or dichromate for passivation, and finally cleaned again with deionized water and dried. Dry. Then, cut off 275mm wide material from both sides of the PET strip in the width direction to obtain a 1200mm wide negative electrode current collector.
- PET tape with a thickness of 4.5 ⁇ m and a width of 1200mm;
- the roughening liquid between °C ⁇ 50 °C is applied to the middle 800mm width range of the PET strip for chemical roughening. After roughening, it is washed with deionized water at 40 °C ⁇ 50 °C and dried with hot air. ; Then apply a sensitizing activating liquid on the roughened area by gravure coating.
- the sensitizing activating liquid contains palladium chloride 0.5g/L ⁇ 1.5g/L and stannous chloride 30g/L ⁇ 40g/ L, palladium colloidal solution of concentrated hydrochloric acid 260g/L ⁇ 320ml/L. After activation, and then cleaning with an aqueous solution containing 35g/L to 55g/L sulfuric acid, the area within the 800mm width range in the middle of the PET strip can become the active area 201;
- the temperature of electroless nickel plating is generally controlled between 75°C and 90°C.
- the metal plating solution contains 23g/L to 30g/L of nickel sulfate.
- An aqueous solution of sodium hypophosphite 25g/L ⁇ 35g/L, malic acid 15g/L ⁇ 23g/L, sodium acetate 12g/L ⁇ 24g/L and a small amount of other additives with a pH of 4.8 ⁇ 5.6.
- the conveying speed of PET tape is approximately 35m/min. After electroless nickel plating, a nickel-containing metal film 221 will be obtained in the activation area 201;
- the PET tape is cleaned with an aqueous solution containing 35g/L ⁇ 55g/L sulfuric acid, it is then immersed in a metal electroless plating solution for electroless copper plating.
- the temperature of electroless copper plating is generally controlled between 65°C and 73°C.
- the metal plating solution The pH contains copper sulfate 10g/L ⁇ 15g/L, EDTA disodium salt 38g/L ⁇ 47g/L, formaldehyde 3.5g/L ⁇ 4.5ml/L, and sodium hydroxide 2.6g/L ⁇ 3.7g/L. 11.5 ⁇ 12.5 aqueous solution.
- the conveying speed of PET tape is between 30m/min and 50m/min. After electroless copper plating, another layer of copper-containing metal film will be formed on the surface of the original nickel-containing metal film;
- polypropylene with a thickness of 8 ⁇ m and a width of 1600mm, that is, PP tape.
- the tape running speed of the PP tape is about 43m/min;
- the surface is roughened in the middle 1200mm width of the PP tape using femtosecond laser etching, and then sensitized by inkjet printing on the roughened area within the 1200mm width in the middle of the PP tape.
- the sensitization activation solution contains copper sulfate 20g/L ⁇ 30g/L, gelatin 8g/L ⁇ 12g/L, sodium borohydride 6g/L ⁇ 9g/L, n-butanol 15g/L ⁇ 25ml/L copper colloid solution. After activation, it is cleaned with an aqueous solution containing 35g/L ⁇ 55g/L concentrated sulfuric acid, so that the area within the width of 1200mm in the middle of the PP material belt can become the active area 201;
- the metal layer 220 with a predetermined thickness can be formed in the active area 201 by performing electroless plating, brush plating and passivation in the same manner as in preparing the first type of negative electrode current collector. Then, cut off 250mm wide material on both sides of the PP strip in the width direction to obtain a negative electrode current collector with a width of 1100mm.
- the sheet resistivity of the three negative electrode current collectors prepared by the above composite current collector preparation method all meet the needs of lithium batteries, and the through rate reaches 95% to 98%, the yield rate reaches more than 97%, and the preparation speed can be Reach 30m/min ⁇ 50m/min. It can be seen that the above composite current collector preparation method has high The advantages of high product yield and high efficiency.
- the plating method that combines electroless plating and electroplating is not suitable for forming the metal layer 220 containing aluminum, that is, it is not suitable for preparing the positive electrode current collector.
- the above step S130 includes: performing electroless plating on the base material strip 210 to form a metal layer 220 with a predetermined thickness in the active area 201 .
- the electroplating process is omitted, so the electroless plating time needs to be appropriately extended.
- the metal electroless plating solution may be a molten salt aluminum plating solution, etc.
- an aluminum layer, an aluminum alloy layer, or a multi-layer composite structure containing aluminum with a predetermined thickness can be directly formed in the active area 201 .
- the above composite current collector preparation method will be described below in conjunction with a specific preparation process of the positive electrode current collector:
- PET tape with a thickness of 6 ⁇ m and a width of 1750mm.
- the running speed of the PET tape is about 40m/min;
- Sensitization activation liquid is an aqueous solution containing 1g/L to 2g/L AgNO 3 . After the sensitization activation liquid is coated, the surface is activated through double-sided ultraviolet irradiation, so that the area within the width of 1300mm in the middle of the PET strip can become the active area 201;
- the surface-activated PET strip is immersed in a metal electroless plating solution for electroless aluminum plating.
- the temperature of electroless plating is generally controlled between 15°C and 45°C.
- the metal electroless plating solution is AlCl3-EMIC.
- the temperature of the PET strip is The tape transport speed is also about 40m/min.
- an active area 201 is formed in the middle of the surface of the base material strip 210 through selective pretreatment, and a blank area 202 is formed on both sides of the base material strip 210 along the width direction.
- the blank area 202 is unused.
- the edges on both sides of the base material strip 210 will not be damaged.
- the operation is only performed on the active area 201, and the metal layer 220 is not formed on the blank area 202.
- damage such as perforations to the base material strip 210 often occurs at the edges of the metal layer 220 .
- the damage to the edge of the base material strip 210 can be minimized during the preparation process, thereby maintaining a high mechanical strength of the base material strip 210 . Moreover, the damage at the edge of the metal layer 220 can be subsequently removed. Therefore, the above composite current collector preparation method can significantly improve the yield rate.
- the composite current collector 200 prepared by the above method also has the following advantages: the base material strip 210 of polymer material is used as a support, which reduces the use of metal and can reduce the weight by 40% ⁇ 70%, which increases the energy density of the battery and has the potential to reduce costs in the face of rising metal prices; and it can also improve the flexibility and processing performance of the composite current collector 200. Finally, under abnormal operating conditions, such as internal short circuit, physical puncture, etc., the composite current collector 200 can be disconnected, thereby improving the safety performance of the battery.
- the present disclosure also provides a composite current collector preparation device, which can perform the above composite current collector preparation method, thereby preparing the composite current collector 200 as shown in FIG. 1 .
- the composite current collector preparation device 300 includes an unwinding mechanism 310 , a pretreatment mechanism 320 , a coating mechanism 330 and a trimming mechanism 340 .
- the unwinding mechanism 310 is used to provide the base material strip 210; the pretreatment mechanism 320 is used to form an active area 201 in the middle of the surface of the base material strip 210, and to form a blank area 202 on both sides of the edge in the width direction of the surface of the base material strip 210,
- the active area 201 and the blank area 202 are strip-shaped and extend along the length of the base material strip 210. extending in the direction;
- the coating mechanism 330 is used to form the metal layer 220 in the active area 201; the trimming mechanism 340 is used to cut off the edge portions or blank areas 202 on both sides of the metal layer 220 along the width direction to prepare the composite current collector 200.
- the functions of the unwinding mechanism 310, the pretreatment mechanism 320, the coating mechanism 330 and the trimming mechanism 340 respectively correspond to the specific processes of steps S110 to S140 of the above composite current collector preparation method, so they will not be described again here. .
- the composite current collector preparation device 300 further includes a winding mechanism 350 .
- the unwinding mechanism 310 can continuously unwind the base material strip 210; and the winding mechanism 350 can continuously wind up the composite current collector 200.
- the pretreatment mechanism 320 and the coating mechanism 330 are arranged between the unwinding mechanism 310 and the rewinding mechanism 350 . It can be seen that the composite current collector preparation device 300 can realize the continuous roll-to-roll production of the composite current collector 200, thereby helping to improve efficiency.
- the base material belt 210 can be maintained at a high level.
- the mechanical strength enables the base material tape 210 to withstand greater tension during the winding process and is less likely to break, significantly improving the yield rate.
- the unwinding mechanism 310 includes an unwinding roller 311 , a first tape splicing device 312 , a first deviation correction device 313 and a first tension adjustment device 314 .
- the base material tape 210 can be stored in the form of a roll on the unwinding roller 311 and unrolled by the unwinding shaft 311.
- the first tape splicing device 312 can ensure the continuity of the unwinding of the base material tape 210.
- the first tension adjustment device 314 is generally composed of a plurality of rollers, and the relative distance between the plurality of rollers is adjustable. When the belt running speed of each process fluctuates, multiple rollers can cache or release the base material belt 210 by moving closer or farther away from each other, thereby maintaining the stability of the tension of the base material belt 210 .
- the unwinding mechanism 310 in order to change the running direction of the base material tape 210, generally also includes a plurality of guide rollers (not labeled in the figure).
- the structure of the rewinding mechanism 350 is substantially the same as that of the unwinding mechanism 310, and only the tape running direction is different, so the details will not be described again here.
- the winding mechanism 350 can also be provided with an edge trimming assembly 341 and an edge material collection assembly 342 (see Figure 4).
- the trimming assembly 314 can cut off the blank area 202 in the base material strip 210 from the composite current collector 200 , and the trimming assembly 342 collects the cut-off waste.
- the width of the cutout is larger than the width of the blank area 202 , so that the defective portions on the edge of the metal layer 220 can be cut off together, thereby obtaining a composite current collector 200 with better quality.
- the pretreatment mechanism 320 includes a roughening treatment mechanism 321 and an activation treatment mechanism 322.
- the roughening treatment mechanism 321 is used to roughen the middle part of the surface of the base material strip 210 to form a microstructure;
- the activation treatment mechanism 322 is used to apply sensitization activation on the roughened area of the base material strip 210 surface. liquid to form the active area 201.
- the roughening processing mechanism 321 can roughen the surface of the base material belt 210 by physical roughening or chemical roughening.
- the roughening processing mechanism 321 includes a physical roughening component 3211 and guide rollers 3212 located at the upstream and downstream ends of the material roughening component 3211 .
- the physical roughening components 3211 are generally provided with two opposite ones, which are used to roughen both sides of the base material strip 210 at the same time.
- the physical roughening component 3211 may be a laser emitter, an ultraviolet emitter, a plasma emitter, a corona component, etc.
- the base material strip 210 unrolled by the unwinding mechanism 310 can enter the working range of the physical roughening assembly 3211 after being guided by the guide roller 3212 at the upstream end to roughen the middle part of the surface of the base material strip 210. After the roughening is completed, the base material strip 210 is unrolled by the downstream end.
- the guide roller 3212 at the end guides the base material strip 210 out.
- the roughening treatment mechanism 321 includes an oil removal pool 3213, at least two chemical roughening coating devices 3214, a first drying and heating device 3215, and a second tension adjustment device 3216. and the first cleaning pool 3217.
- the chemical roughening coating device 3214 can use gravure coating, inkjet printing, extrusion coating, spray coating, etc. to coat the chemical roughening liquid.
- the chemical roughening liquid can be made of hydrogen peroxide, sulfuric acid, chromic acid, high One or more aqueous solutions of potassium manganate.
- the heating method of the first drying heating device 3215 may be hot air heating, infrared heating, laser heating or a combination thereof.
- the roughening processing mechanism 321 is generally provided with a plurality of guide rollers (not labeled) to change the conveyor belt conveyor direction of the base material belt 210 .
- the output end of each degreasing pool 3213 and the first cleaning pool 3217 is also provided with a liquid catching roller (not labeled).
- the cleaning agent in the first cleaning pool 3217 It can be deionized water.
- the activation treatment mechanism 322 includes at least two activation liquid coating devices 3221, an activation and drying heating device 3222, a third tension adjustment device 3223, and a second cleaning pool 3224.
- the activation liquid coating device 3221 can apply the activation sensitizing liquid using gravure coating, inkjet printing, extrusion coating, spray coating, etc.
- the sensitizing activating liquid can contain copper, tin, silver, platinum, palladium, manganese An aqueous solution of one or more ions or colloids.
- the activation and drying heating device 3222 can be activated by heating, ultraviolet irradiation, and the heating method can be hot air heating, infrared heating, laser heating or a combination thereof.
- the activation treatment mechanism 322 is also generally provided with a plurality of guide rollers (not labeled) to change the direction of the base material belt 210 .
- the output end of each second cleaning tank 3224 is also provided with a liquid-catching roller (not labeled), and the cleaning agent in the second cleaning tank 3224 can be deionized water.
- the coating mechanism 330 includes an electroless plating mechanism 331 and an electroplating mechanism 332 .
- the electroless plating mechanism 331 is used to perform electroless plating on the base material strip 210 to form a metal film 221 attached to the active area 201;
- the electroplating mechanism 332 is used to perform electroplating on the electroless plated base material strip 210 to form a metal film 221 on the base material strip 210.
- a metal layer 220 with a predetermined thickness is formed on the surface.
- the above-mentioned coating mechanism 330 is generally only suitable for preparing the negative electrode current collector, and the produced metal layer 220 is a copper layer, a copper alloy layer, or a multi-layer composite structure containing copper.
- the electroless plating mechanism 331 includes an electroless plating liquid pool 3311, a stirring device 3312 and a temperature control device 3313 disposed in the electroless plating liquid pool 3311, a fourth tension adjustment device 3314, The third cleaning tank 3315, the drying device 3316 and the online thickness measurement device 3317.
- the stirring device 3312 can be paddle stirring, ultrasonic stirring or airflow stirring.
- the online thickness measuring device 3317 adopts non-contact thickness measurement, which can be laser thickness measurement, X-ray thickness measurement, ⁇ -ray thickness measurement, eddy current or resistance value. Measure thickness.
- the electroless plating mechanism 331 is generally provided with a plurality of guide rollers (not labeled) to change the tape conveyor direction of the base material tape 210 .
- a liquid catching roller (not labeled) is also provided at the output end of each chemical plating bath 3311 and the third cleaning bath 3315.
- the cleaning agent in the third cleaning bath 3315 It can be deionized water.
- the electroplating mechanism 332 in this embodiment uses brush plating equipment. Please refer to Figure 11 together. Specifically, in this embodiment, the electroplating mechanism 332 includes a cathode roller device 3321, an anode brush device 3322, a power control device 3323, a plating solution supply and recovery device 3324, a fourth cleaning pool 3325, a second Drying device 3326 and second online thickness measurement device 3327.
- cathode roller devices 3321 and two anode brush devices 3322 which are used to coat the front and back sides of the base material strip 210 respectively.
- the cathode roller device 3321, the anode brush device 3322, and the power supply control device 3323 are connected and controlled through electric circuits.
- the cathode roller device 3321 includes a non-conductive cathode back roller and a conductive cathode roller; the shape of the anode brush device 3322 matches the shape of the cathode roller device 3321 and includes an anode back roller and an anode wrap.
- the anode cover can be made of porous fabric.
- the plating solution supply and recovery device 3324 includes a plating solution storage tank, a stirring component, a temperature control component, a plating solution recovery tank, a filter device, a solution supply pump and a nozzle.
- the second drying device 3326 and the second online thickness measuring device 3327 have the same structures and functions as the above-mentioned drying device 3316 and the online thickness measuring device 3317 respectively.
- the electroplating mechanism 332 is generally provided with a plurality of guide rollers (not labeled) to change the tape conveyor direction of the base material tape 210 .
- the output end of each fourth cleaning pool 3325 is also provided with a liquid-collecting roller (not labeled), and the cleaning agent in the fourth cleaning pool 3325 can be deionized water.
- the electroless plating mechanism 331 and the electroplating mechanism 332 can both be electroless plating equipment and electroplating equipment commonly used in the prior art, so the specific structures and working processes of the electroless plating mechanism 331 and the electroplating mechanism 332 will not be described again.
- Electroless plating can smoothly form a thin metal film 221 on the surface of the non-metallic base material strip 210, thereby providing a basis for the subsequent formation of the metal layer 220.
- the environment of electroless plating is relatively mild, and the impact on the surface of the base material strip 210 is smaller.
- the electroplating process is more efficient when forming the metal layer 220, and the formed metal layer 220 is denser and has better conductivity. Therefore, the coating mechanism 330 can combine the advantages of both electroless plating and electroplating processes.
- the film forming conditions of the electroless plating mechanism 331 and the electroplating mechanism 332 are less different, making it easier to connect them into a complete roll-to-roll production line.
- the material strip of the base material strip 210 can directly enter the electroplating mechanism 332 from the output end of the electroless plating mechanism 331. During this process, buffering for a long time can be avoided, thereby effectively preventing water and oxygen in the air from forming an oxide film on the surface of the base material strip 210. , ensuring the quality of the final product.
- the coating mechanism 330 that combines electroless plating and electroplating is not suitable for forming the metal layer 220 containing aluminum, that is, it is not suitable for preparing the positive electrode current collector.
- the coating mechanism 330 in another embodiment of the present disclosure can perform electroless plating on the base material strip 210 to form a metal layer 220 with a predetermined thickness in the active area 201 .
- the coating mechanism 330 omits the electroplating process, so it is suitable for the preparation of positive electrode current collectors.
- the coating mechanism 330 can directly use electroless plating equipment commonly used in the prior art, and the type of metal electroless plating liquid used in the electroless plating process is also different from the previous embodiment.
- the metal electroless plating solution may be a molten salt aluminum plating solution, etc.
- the coating The mechanism 330 can directly form an aluminum layer, an aluminum alloy layer, or a multi-layer composite structure containing aluminum with a predetermined thickness in the active area 201 .
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Abstract
A composite current collector manufacturing method and manufacturing device. By means of selective pretreatment, an active area is formed in the middle portion of the surface of a base material belt, and blank areas will not be treated during the pretreatment process, thus the edges on the two sides of the base material belt will not be damaged. Moreover, during the process of forming a metal layer, only the active area is operated, and no metal layer will form on the blank areas. However, when the metal layer is formed, damages such as piercing to the base material belt often occur at the edge position of the metal layer.
Description
本公开要求于2022年09月06日提交中国专利局,申请号为202211083947.4、申请名称为“复合集流体制备方法及制备装置”以及申请号为202222368203.9、申请名称为“复合集流体制备装置”的中国专利申请的优先权,其全部内容通过引用结合在本公开中。This disclosure request was submitted to the China Patent Office on September 6, 2022, with application number 202211083947.4 and application name "Composite Current Collector Preparation Method and Preparation Device" and application number 202222368203.9 and application name "Composite Current Collector Preparation Device" Priority to the Chinese patent application, the entire contents of which are incorporated into this disclosure by reference.
本公开涉及一种复合集流体制备方法及制备装置。The present disclosure relates to a composite current collector preparation method and preparation device.
相关技术中,真空物理气相沉积伴随着高温,基材在高温环境下很容易出现变形、起皱、窜泡、穿孔、变脆等问题。而且,基材非常轻薄,真空溅射时高能粒子的冲击、化学镀时的腐蚀以及电镀时的边缘电流效应均易导致基材出现穿孔及破损。特别是在卷对卷制备的过程中,由于基材需承受走带的张力,故基材边缘的损伤极易导致料带断带。因此,现有的方法在制备复合集流体时导致良品率较低。In related technologies, vacuum physical vapor deposition is accompanied by high temperatures, and the substrate is prone to problems such as deformation, wrinkles, bubbles, perforations, and brittleness in high-temperature environments. Moreover, the substrate is very light and thin, and the impact of high-energy particles during vacuum sputtering, corrosion during electroless plating, and edge current effects during electroplating can easily cause perforation and damage to the substrate. Especially in the roll-to-roll preparation process, since the substrate needs to withstand the tension of the tape, damage to the edges of the substrate can easily lead to tape breakage. Therefore, existing methods lead to low yields when preparing composite current collectors.
发明内容Contents of the invention
基于此,有必要针对上述问题,提供一种能够提升良品率的复合集流体制备方法及制备装置。Based on this, it is necessary to address the above problems and provide a composite current collector preparation method and preparation device that can improve the yield rate.
一种复合集流体制备方法,包括步骤:
A composite current collector preparation method, including the steps:
提供基材料带;Provide base material tape;
在所述基材料带表面的中部形成活性区域,并在所述基材料带沿宽度方向的两侧边缘形成留白区域,所述活性区域及所述留白区域均呈条形并沿所述基材料带的长度方向延伸;An active area is formed in the middle of the surface of the base material strip, and a blank area is formed on both sides of the base material strip along the width direction. The active area and the blank area are both strip-shaped and extend along the The lengthwise extension of the strip of base material;
在所述活性区域形成金属层;forming a metal layer in the active area;
切除所述金属层沿宽度方向两侧的边缘部分或所述留白区域,以制得复合集流体。The edge portions or the blank areas on both sides of the metal layer along the width direction are cut off to prepare a composite current collector.
在其中一个实施例中,在所述基材料带表面的中部形成活性区域,并在所述基材料带沿宽度方向的两侧边缘形成留白区域的步骤包括:In one embodiment, the step of forming an active area in the middle of the surface of the base material strip and forming a blank area on both sides of the base material strip along the width direction includes:
对所述基材料带表面的中部进行粗化处理;Roughening the middle part of the surface of the base material strip;
在粗化处理后的区域涂覆敏化活化液,以形成所述活性区域;Apply a sensitizing activation liquid to the roughened area to form the active area;
其中,所述基材料带沿宽度方向的两侧边缘未经粗化处理且未涂覆敏化活化液的区域形成所述留白区域。Wherein, the areas on both sides of the base material strip along the width direction that have not been roughened and have not been coated with the sensitizing activating liquid form the blank area.
在其中一个实施例中,对所述基材料带表面的中部进行粗化处理的步骤包括:对所述基材料带表面的多个条形区域进行粗化处理,所述条形区域位于所述基材料带表面的中部,且沿所述基材料带的宽度方向间隔设置;In one of the embodiments, the step of roughening the middle part of the surface of the base material strip includes: roughening a plurality of strip-shaped areas on the surface of the base material strip, the strip-shaped areas being located on the surface of the base material strip. The middle part of the surface of the base material strip, and arranged at intervals along the width direction of the base material strip;
其中,在粗化处理后的所述条形区域涂覆敏化活化液以形成所述活性区域,相邻所述条形区域之间未经粗化处理且未涂覆敏化活化液的区域形成所述留白区域。Wherein, the strip-shaped area after roughening treatment is coated with a sensitizing activation liquid to form the active area, and the area between the adjacent strip-shaped areas is not roughened and is not coated with the sensitizing activation liquid. Create the blank area.
在其中一个实施例中,所述复合集流体包括负极复合集流体,在所述活性区域形成金属层的步骤包括:In one embodiment, the composite current collector includes a negative electrode composite current collector, and the step of forming a metal layer in the active region includes:
对所述基材料带进行化学镀,以形成附着于所述活性区域的金属膜;Electroless plating is performed on the base material strip to form a metal film attached to the active area;
对经过化学镀的所述基材料带进行电镀,以在所述金属膜的表面形成预设
厚度的所述金属层。The electroless plated base material strip is electroplated to form a predetermined surface on the surface of the metal film. thickness of the metal layer.
在其中一个实施例中,采用电刷镀的方式对所述基材料带进行电镀。In one embodiment, the base material strip is electroplated using brush plating.
在其中一个实施例中,所述复合集流体包括正极复合集流体,在所述活性区域形成金属层的步骤包括:对所述基材料带进行化学镀,以在所述活性区域形成预设厚度的所述金属层。In one embodiment, the composite current collector includes a positive electrode composite current collector, and the step of forming a metal layer in the active area includes: electroless plating the base material strip to form a predetermined thickness in the active area. of the metal layer.
在其中一个实施例中,在所述活性区域形成金属层的步骤之后,还包括步骤:在所述金属层的背离所述基材料带的表面形成抗氧化层。In one embodiment, after the step of forming a metal layer in the active area, the step further includes: forming an anti-oxidation layer on a surface of the metal layer facing away from the base material strip.
在其中一个实施例中,以连续走带的方式对所述基材料带进行放卷;以连续走带的方式对制得的所述复合集流体进行收卷。In one of the embodiments, the base material tape is unwound in a continuous tape conveying manner; and the prepared composite current collector is wound up in a continuous tape conveying manner.
一种复合集流体制备装置,包括:A composite current collector preparation device, including:
放卷机构,用于提供基材料带;Unwinding mechanism for supplying strips of base material;
预处理机构,用于在所述基材料带表面的中部形成活性区域,并在所述基材料带沿宽度方向的两侧边缘形成留白区域,所述活性区域及所述留白区域均呈条形并沿所述基材料带的长度方向延伸;A pretreatment mechanism is used to form an active area in the middle of the surface of the base material strip, and to form a blank area on both sides of the base material strip along the width direction. The active area and the blank area are both in the shape of Strip shape and extending along the length direction of the base material strip;
镀膜机构,用于在所述活性区域形成金属层;A coating mechanism used to form a metal layer in the active area;
切边机构,用于切除所述金属层沿宽度方向两侧的边缘部分或所述留白区域,以制得复合集流体。An edge cutting mechanism is used to cut off the edge portions or the blank areas on both sides of the metal layer along the width direction to prepare a composite current collector.
在其中一个实施例中,所述放卷机构能够连续放卷所述基材料带,所述复合集流体制备装置还包括及收卷机构,所述收卷机构能够连续收卷所述复合集流体。In one embodiment, the unwinding mechanism can continuously unwind the base material strip, and the composite current collector preparation device further includes a rewinding mechanism, and the rewinding mechanism can continuously rewind the composite current collector. .
上述复合集流体制备方法及制备装置,通过选择性预处理在基材料带表面的中部形成活性区域,并在基材料带沿宽度方向的两侧边缘形成留白区域,留白区域为未经过处理的区域,故基材料带两侧的边缘不会被损伤。而且,在形
成金属层的过程中,也只是针对活性区域进行操作,留白区域并不形成金属层。而在形成金属层时对基材料带所造成的穿孔等损伤,往往出现在金属层的边缘位置。可见,制备过程中能够尽量减少对基材料带边缘的损伤,从而保持基材料带较高的机械强度。而且,金属层边缘位置的损伤可后续切除。因此,上述复合集流体制备方法能够显著提升良品率。The above-mentioned composite current collector preparation method and preparation device form an active area in the middle of the surface of the base material strip through selective pretreatment, and form a blank area on both sides of the base material strip along the width direction. The blank area is unprocessed area, so the edges on both sides of the base material strip will not be damaged. Moreover, in shape In the process of forming a metal layer, the operation is only performed on the active area, and no metal layer is formed on the blank area. When the metal layer is formed, damage such as perforations to the base material strip often appears at the edge of the metal layer. It can be seen that the damage to the edge of the base material strip can be minimized during the preparation process, thereby maintaining a high mechanical strength of the base material strip. Moreover, damage at the edge of the metal layer can be subsequently removed. Therefore, the above composite current collector preparation method can significantly improve the yield rate.
为了更清楚地说明本申请实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to explain the embodiments of the present application or the technical solutions in the prior art more clearly, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are only These are some embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting creative efforts.
图1为本公开一个实施例中所制备的复合集流体的结构示意图;Figure 1 is a schematic structural diagram of a composite current collector prepared in an embodiment of the present disclosure;
图2为本公开一个实施例中复合集流体制备方法的流程示意图;Figure 2 is a schematic flow chart of a composite current collector preparation method in one embodiment of the present disclosure;
图3为图2所示复合集流体制备方法对应的加工场景示意图;Figure 3 is a schematic diagram of the processing scene corresponding to the composite current collector preparation method shown in Figure 2;
图4为图3所示的场景(d)到场景(e)的细节示意图;Figure 4 is a detailed schematic diagram of scene (d) to scene (e) shown in Figure 3;
图5为本公开一个实施例中复合集流体制备装置的模块示意图;Figure 5 is a module schematic diagram of a composite current collector preparation device in one embodiment of the present disclosure;
图6为图5所示复合集流体制备装置中放卷机构的结构示意图;Figure 6 is a schematic structural diagram of the unwinding mechanism in the composite current collector preparation device shown in Figure 5;
图7为图5所示复合集流体制备装置中粗化处理机构的结构示意图;Figure 7 is a schematic structural diagram of the roughening treatment mechanism in the composite current collector preparation device shown in Figure 5;
图8为另一个实施例中粗化处理机构的结构示意图;Figure 8 is a schematic structural diagram of a roughening processing mechanism in another embodiment;
图9为图5所示复合集流体制备装置中活化处理机构的结构示意图;Figure 9 is a schematic structural diagram of the activation treatment mechanism in the composite current collector preparation device shown in Figure 5;
图10为图5所示复合集流体制备装置中化学镀机构的结构示意图;Figure 10 is a schematic structural diagram of the electroless plating mechanism in the composite current collector preparation device shown in Figure 5;
图11为图5所示复合集流体制备装置中电镀机构的结构示意图;Figure 11 is a schematic structural diagram of the electroplating mechanism in the composite current collector preparation device shown in Figure 5;
图12为另一个实施例中复合集流体制备装置的模块示意图;
Figure 12 is a module schematic diagram of a composite current collector preparation device in another embodiment;
图13为另一个实施例中所制得的复合集流体的俯视图;Figure 13 is a top view of a composite current collector produced in another embodiment;
图14为图13所示复合集流体的截面示意图。FIG. 14 is a schematic cross-sectional view of the composite current collector shown in FIG. 13 .
为使本公开的上述目的、特征和优点能够更加明显易懂,下面结合附图对本公开的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本公开。但是本公开能够以很多不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本公开内涵的情况下做类似改进,因此本公开不受下面公开的具体实施例的限制。In order to make the above objects, features and advantages of the present disclosure more obvious and understandable, specific implementation modes of the present disclosure will be described in detail below with reference to the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. However, the present disclosure can be implemented in many other ways than those described here, and those skilled in the art can make similar improvements without violating the connotation of the present disclosure. Therefore, the present disclosure is not limited by the specific embodiments disclosed below.
在本公开的描述中,需要理解的是,术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“顺时针”、“逆时针”、“轴向”、“径向”、“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系,仅是为了便于描述本公开和简化描述,而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作,因此不能理解为对本公开的限制。In the description of the present disclosure, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", " "Back", "Left", "Right", "Vertical", "Horizontal", "Top", "Bottom", "Inside", "Outside", "Clockwise", "Counterclockwise", "Axis" The orientation or positional relationship indicated by "radial direction", "circumferential direction", etc. is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present disclosure and simplifying the description, rather than indicating or implying the device or device to which it is referred. Elements must have a specific orientation, be constructed and operate in a specific orientation and therefore are not to be construed as limitations on the disclosure.
此外,术语“第一”、“第二”仅用于描述目的,而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此,限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本公开的描述中,“多个”的含义是至少两个,例如两个,三个等,除非另有明确具体的限定。In addition, the terms “first” and “second” are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of the present disclosure, "plurality" means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.
在本公开中,除非另有明确的规定和限定,术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解,例如,可以是固定连接,也可以是可拆卸连接,或成一体;可以是机械连接,也可以是电连接;可以是直接相连,也可以通过中间媒介间接相连,可以是两个元件内部的连通或两个元件的相互作用关系,除非另有明确的限定。对于本领域的普通技术人员而言,可以根据具体情况理解上述术语在本公开中的具体含义。In this disclosure, unless otherwise explicitly stated and limited, the terms "installation", "connection", "connection", "fixing" and other terms should be understood in a broad sense. For example, it can be a fixed connection or a detachable connection. , or integrated; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be an internal connection between two elements or an interactive relationship between two elements, unless otherwise specified limitations. For those of ordinary skill in the art, the specific meanings of the above terms in this disclosure can be understood according to specific circumstances.
在本公开中,除非另有明确的规定和限定,第一特征在第二特征“上”或
“下”可以是第一和第二特征直接接触,或第一和第二特征通过中间媒介间接接触。而且,第一特征在第二特征“之上”、“上方”和“上面”可是第一特征在第二特征正上方或斜上方,或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”可以是第一特征在第二特征正下方或斜下方,或仅仅表示第一特征水平高度小于第二特征。In this disclosure, unless expressly stated and limited otherwise, a first feature is "on" or "on" a second feature. "Lower" may mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediary. Furthermore, the terms "above", "above" and "above" the first feature is above the second feature may mean that the first feature is directly above or diagonally above the second feature, or simply means that the first feature is higher in level than the second feature. "Below", "below" and "beneath" the first feature to the second feature may mean that the first feature is directly below or diagonally below the second feature, or simply means that the first feature has a smaller horizontal height than the second feature.
需要说明的是,当元件被称为“固定于”或“设置于”另一个元件,它可以直接在另一个元件上或者也可以存在居中的元件。当一个元件被认为是“连接”另一个元件,它可以是直接连接到另一个元件或者可能同时存在居中元件。本文所使用的术语“垂直的”、“水平的”、“上”、“下”、“左”、“右”以及类似的表述只是为了说明的目的,并不表示是唯一的实施方式。It should be noted that when an element is referred to as being "mounted" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. When an element is said to be "connected" to another element, it can be directly connected to the other element or there may also be intervening elements present. The terms "vertical", "horizontal", "upper", "lower", "left", "right" and similar expressions used herein are for illustrative purposes only and do not represent the only implementation manner.
本公开提供了一种复合集流体制备方法,该方法用于制备如图1所示的复合集流体200。其中,复合集流体200包括基材料带210及位于基材料带210相对两个表面的金属层220。The present disclosure provides a composite current collector preparation method, which is used to prepare the composite current collector 200 as shown in FIG. 1 . The composite current collector 200 includes a base material strip 210 and metal layers 220 located on two opposite surfaces of the base material strip 210 .
基材料带210为绝缘材料,可以是聚对苯二甲酸乙二醇酯、聚丙烯、聚酰胺、聚酰亚胺、聚氯乙烯及聚苯乙烯等聚合物材料中的任一种。基材料带210呈薄膜状,起支撑作用,其厚度一般在2μm至12μm之间。金属层220则起导电作用,其厚度一般在700nm至2000nm之间。复合集流体200既可以用于锂电池的正极,也可以用于锂电池的负极,区别在于金属层220的材质不同。The base material tape 210 is an insulating material, and may be any polymer material such as polyethylene terephthalate, polypropylene, polyamide, polyimide, polyvinyl chloride, and polystyrene. The base material strip 210 is in the shape of a film and plays a supporting role, and its thickness is generally between 2 μm and 12 μm. The metal layer 220 plays a conductive role, and its thickness is generally between 700nm and 2000nm. The composite current collector 200 can be used as either a positive electrode or a negative electrode of a lithium battery. The difference is that the materials of the metal layer 220 are different.
复合集流体200作为负极集流体时,金属层220的材质一般为铜或铜合金。此外,金属层220还可以是铜的质量比不少于80%的多层复合结构。而复合集流体200作为正极集流体时,金属层220的材质一般为铝或铝合金。同样的,金属层220也可以是铝的质量比不少于80%的多层复合结构。When the composite current collector 200 is used as a negative electrode current collector, the material of the metal layer 220 is generally copper or copper alloy. In addition, the metal layer 220 may also be a multi-layer composite structure in which the mass ratio of copper is not less than 80%. When the composite current collector 200 is used as a positive electrode current collector, the material of the metal layer 220 is generally aluminum or aluminum alloy. Similarly, the metal layer 220 can also be a multi-layer composite structure with a mass ratio of aluminum of not less than 80%.
请参阅图2及图3,本公开一个实施例中的复合集流体制备方法包括步骤S110至S140。
Referring to FIG. 2 and FIG. 3 , the composite current collector preparation method in one embodiment of the present disclosure includes steps S110 to S140.
步骤S110,提供基材料带210。Step S110, providing a base material tape 210.
具体的,基材料带210一般以料带的形式进行放卷,可预先制备并存储于放卷轴。提供的基材料带210沿预设方向走带,走带方向即为基材料带210的长度方向,与长度向垂直的方向即为基材料带210的宽度方向。该步骤对应图3所示的场景(a)。Specifically, the base material tape 210 is generally unrolled in the form of a material tape, and can be prepared in advance and stored on the unwinding reel. The provided base material tape 210 runs along a preset direction, the tape running direction is the length direction of the base material tape 210 , and the direction perpendicular to the length direction is the width direction of the base material tape 210 . This step corresponds to scenario (a) shown in Figure 3.
步骤S120,在基材料带210表面的中部形成活性区域201,并在基材料带210表面宽度方向的两侧边缘形成留白区域202,活性区域201及留白区域202呈条形并沿基材料带210的长度方向延伸。Step S120: Form an active area 201 in the middle of the surface of the base material strip 210, and form a blank area 202 on both sides of the surface width direction of the base material strip 210. The active area 201 and the blank area 202 are in a strip shape and extend along the base material. The strip 210 extends lengthwise.
由于基材料带210的材料性质与金属存在显著区别,故其表面对金属材料的附着能力较差,直接在基材料带210表面进行镀膜等操作将难以形成符合要求的金属层220。因此,在镀膜之前需要对基材料带210的表面进行预处理,以得到活性区域201,预处理的目的是增强基材料带210表面对金属材料的附着能力。该步骤对应图3所示的场景(b)。Since the material properties of the base material strip 210 are significantly different from those of metal, its surface has poor adhesion to metal materials. It will be difficult to form a metal layer 220 that meets the requirements by directly coating the surface of the base material strip 210 . Therefore, the surface of the base material strip 210 needs to be pre-treated before coating to obtain the active area 201. The purpose of the pre-treatment is to enhance the adhesion ability of the surface of the base material strip 210 to the metal material. This step corresponds to scenario (b) shown in Figure 3.
需要指出的是,预处理时并不会对基材料带210表面的整面进行处理。具体的,预处理只针对基材料带210表面的中部区域,处理过的区域即为活性区域201,对金属材料的附着能力得到提升。而对于基材料带210表面宽度方向的两侧边缘并不进行预处理,从而形成留白区域202。这样,基材料带210两侧的边缘在预处理的过程中一般不会被损伤,从而避免或减少基材料带210的边缘出现穿孔等缺陷。其中,中部区域指的是基材料带210两侧的留白区域202之间的区域。It should be pointed out that the entire surface of the base material strip 210 is not processed during pretreatment. Specifically, the pretreatment only targets the middle area of the surface of the base material strip 210. The treated area is the active area 201, and the adhesion ability to metal materials is improved. However, no preprocessing is performed on both sides of the surface width direction of the base material strip 210, thereby forming a blank area 202. In this way, the edges on both sides of the base material strip 210 will generally not be damaged during the preprocessing process, thereby avoiding or reducing defects such as perforations on the edges of the base material strip 210 . The middle area refers to the area between the blank areas 202 on both sides of the base material strip 210 .
活性区域201及留白区域202均沿基材料带210的长度延伸。通常情况下,活性区域201为一体且位于基材料带210的中间区域,留白区域202则仅分布于基材料带210的两侧,从而制得的复合集流体200为如图3中(e)所示的单
条结构。Both the active area 201 and the blank area 202 extend along the length of the base material strip 210 . Normally, the active area 201 is integrated and located in the middle area of the base material strip 210, while the blank areas 202 are only distributed on both sides of the base material strip 210. The resulting composite current collector 200 is as shown in Figure 3 (e ) shown in the order bar structure.
此外,在其他实施例中,也可以在基材料带210的表面形成多个沿基材料带210的宽度方向间隔设置的活性区域201,除了分布于基材料带210宽度方向两侧的留白区域202,相邻两个活性区域201之间也形成有留白区域202。因此,制得的复合集流体200为如图13及图14所示的类似斑马条纹的多条结构。In addition, in other embodiments, a plurality of active areas 201 spaced along the width direction of the base material band 210 may also be formed on the surface of the base material band 210 , except for the blank areas distributed on both sides of the base material band 210 in the width direction. 202, a blank area 202 is also formed between two adjacent active areas 201. Therefore, the prepared composite current collector 200 has multiple structures similar to zebra stripes as shown in FIGS. 13 and 14 .
在本实施例中,上述步骤120包括:对基材料带210表面的中部进行粗化处理;在基材料带210表面粗化处理后的区域涂覆敏化活化液,以形成活性区域201。In this embodiment, the above-mentioned step 120 includes: roughening the middle part of the surface of the base material strip 210; and applying a sensitizing activation liquid to the roughened area of the surface of the base material strip 210 to form the active area 201.
在粗化处理前,必要时还可以进行除油处理。粗化处理的方式可以是物理粗化,也可以是化学粗化,还可以是物理粗化与化学粗化的组合。物理粗化的具体方式包括对预设区域进行激光刻蚀、紫外照射、等离子照射及电晕处理等。化学粗化的具体方式包括采用含有双氧水、硫酸、铬酸、高锰酸钾中的一种或多种水溶液对预设区域进行浸泡。而且,化学粗化后还可视具体情况进行清洗和烘干。Before roughening treatment, degreasing treatment can also be carried out if necessary. The method of roughening treatment may be physical roughening, chemical roughening, or a combination of physical roughening and chemical roughening. Specific methods of physical roughening include laser etching, ultraviolet irradiation, plasma irradiation and corona treatment on preset areas. The specific method of chemical roughening includes soaking the preset area with one or more aqueous solutions containing hydrogen peroxide, sulfuric acid, chromic acid, and potassium permanganate. Moreover, after chemical roughening, cleaning and drying can be carried out depending on the specific situation.
粗化处理后,相应区域会形成微结构,微结构能够增大基材料带210表面的粗糙度,从而提升对金属材料的附着能力。粗化处理完成后,便可通过精密涂布的方式在粗化处理后的区域涂覆敏化活化液。具体的,敏化活化液可以是包含有铜、锡、银、铂、钯、锰中的一种或多种离子或胶体的水溶液。经过敏化处理后,基材料带210表面中部的区域与金属材料的附着能力进一步增大,从而得到所需的活性区域201。After the roughening process, microstructures will be formed in the corresponding areas, and the microstructures can increase the roughness of the surface of the base material strip 210, thereby improving the adhesion ability to metal materials. After the roughening treatment is completed, the sensitizing activation liquid can be applied to the roughened area through precision coating. Specifically, the sensitization activation liquid may be an aqueous solution containing one or more ions or colloids among copper, tin, silver, platinum, palladium, and manganese. After the sensitization treatment, the adhesion ability between the middle area of the surface of the base material strip 210 and the metal material is further increased, thereby obtaining the required active area 201.
在对基材料带210表面的中部进行活化处理后,还可视情况对基材料带210进行清洗和烘干操作。After activating the middle part of the surface of the base material belt 210, the base material belt 210 may also be cleaned and dried as appropriate.
在另一个实施例中,上述步骤120包括:对基材料带210表面的多个条形
区域进行粗化处理,条形区域位于基材料带210表面的中部,且沿基材料带210的宽度方向间隔设置。其中,在粗化处理后的条形区域涂覆敏化活化液以形成活性区域201,相邻条形区域之间的基材料带210未经粗化处理且未涂覆敏化活化液的区域形成留白区域202。In another embodiment, the above step 120 includes: aligning a plurality of strips on the surface of the base material strip 210 The area is roughened, and the strip-shaped area is located in the middle of the surface of the base material strip 210 and is spaced apart along the width direction of the base material strip 210 . Among them, the sensitizing activating liquid is applied to the roughened strip area to form the active area 201, and the base material strip 210 between adjacent strip areas is not roughened and is not coated with the sensitizing activating liquid. A blank area 202 is formed.
如此,基材料带210表面的活性区域201具有多个且沿基材料带210的宽度方向间隔设置。而留白区域202除了分布于基材料带210宽度方向两侧,相邻两个活性区域201之间也形成有留白区域202。In this way, there are multiple active areas 201 on the surface of the base material strip 210 and they are spaced apart along the width direction of the base material strip 210 . In addition to being distributed on both sides of the width direction of the base material strip 210, the blank areas 202 are also formed between two adjacent active areas 201.
步骤S130,在活性区域201形成金属层220。In step S130, a metal layer 220 is formed in the active area 201.
具体的,可以通过物理气相沉积、化学气相沉积、化学镀、电镀等多种镀膜方式在基材料带210表面的活性区域201形成金属层220。Specifically, the metal layer 220 can be formed on the active area 201 on the surface of the base material strip 210 through various coating methods such as physical vapor deposition, chemical vapor deposition, electroless plating, and electroplating.
在本实施例中,上述步骤S130包括:对基材料带210进行化学镀,以形成附着于活性区域201的金属膜221,该步骤对应图3所示的场景(c);对经过化学镀的基材料带210进行电镀,以在金属膜221的表面形成预设厚度的金属层220,该步骤对应图3所示的场景(d)。In this embodiment, the above-mentioned step S130 includes: performing electroless plating on the base material strip 210 to form a metal film 221 attached to the active area 201. This step corresponds to the scene (c) shown in Figure 3; The base material strip 210 is electroplated to form a metal layer 220 with a predetermined thickness on the surface of the metal film 221. This step corresponds to scene (d) shown in FIG. 3 .
需要指出的是,由于铝的化学性质比较活泼,容易在电镀过程中与氧气结合而快速氧化。因此,上述金属层220的形成方式一般只适用于负极集流体的制备,所制得的金属层220为铜层、铜合金层或含铜的多层复合结构。It should be pointed out that due to the relatively active chemical properties of aluminum, it is easy to combine with oxygen and quickly oxidize during the electroplating process. Therefore, the above-mentioned formation method of the metal layer 220 is generally only suitable for the preparation of the negative electrode current collector. The produced metal layer 220 is a copper layer, a copper alloy layer or a multi-layer composite structure containing copper.
进行化学镀时,可将基材料带210一次或多次浸入金属化学镀液中,金属化学镀液可以是镀铜液、镀镍液或镀铜镍合金液。化学镀后可以形成的金属膜221可以为镀镍层、镀铜层、铜镍合金层或它们的组合。金属膜221的厚度远小于金属层220的厚度,一般在20nm与400nm之间,金属膜221的方块电阻可以为200mΩ/方块~1000mΩ/方块。在化学镀之后及电镀之前,一般还需要对金属膜221进行清洗及烘干。此外,还可在必要时对金属膜221进行酸化处理。
When performing electroless plating, the base material strip 210 can be immersed in a metal electroless plating solution one or more times. The metal electroless plating solution can be a copper plating solution, a nickel plating solution or a copper-nickel alloy plating solution. The metal film 221 that can be formed after electroless plating can be a nickel plating layer, a copper plating layer, a copper-nickel alloy layer, or a combination thereof. The thickness of the metal film 221 is much smaller than the thickness of the metal layer 220, generally between 20nm and 400nm. The sheet resistance of the metal film 221 can be 200mΩ/square to 1000mΩ/square. After electroless plating and before electroplating, the metal film 221 generally needs to be cleaned and dried. In addition, the metal film 221 can also be acidified when necessary.
电镀的作用是在金属膜221的表面继续沉积金属材料,从而在金属膜221的基础上逐渐加厚,直至得到所需厚度的金属层220。示例的,金属层200的厚度可以为700nm~2000nm。此时,金属层200的方块电阻为1mΩ/方块~180mΩ/方块,具有良好的导电性能。金属膜221与金属层220的材质一致时,最终得到的金属层220将与金属膜221融为一体。The function of electroplating is to continue to deposit metal materials on the surface of the metal film 221, thereby gradually thickening the metal film 221 until a metal layer 220 with a required thickness is obtained. For example, the thickness of the metal layer 200 may be 700 nm to 2000 nm. At this time, the sheet resistance of the metal layer 200 is 1 mΩ/square to 180 mΩ/square, and has good electrical conductivity. When the metal film 221 and the metal layer 220 are made of the same material, the finally obtained metal layer 220 will be integrated with the metal film 221 .
化学镀能够顺利在非金属的基材料带210的表面形成较薄的金属膜221,从而对后续金属层220的成型提供基础。而且,相对于物理气相沉积,化学镀的环境较为温和,且对基材料带210表面的冲击较小。而对相较于化学镀,电镀工艺在金属层220成型时效率更高,且形成的金属层220更加致密,导电性也更佳。因此,上述方式能够结合化学镀及电镀两种工艺的优势。Electroless plating can smoothly form a thin metal film 221 on the surface of the non-metallic base material strip 210, thereby providing a basis for the subsequent formation of the metal layer 220. Moreover, compared with physical vapor deposition, the environment of electroless plating is relatively mild, and the impact on the surface of the base material strip 210 is smaller. Compared with electroless plating, the electroplating process is more efficient when forming the metal layer 220, and the formed metal layer 220 is denser and has better conductivity. Therefore, the above method can combine the advantages of both electroless plating and electroplating processes.
进一步的,具体在本实施例中,采用电刷镀的方式对基材料带210进行电镀。由于电刷镀不需要镀槽,故设备简单、占地面积小、成本较低。而且,采用电刷镀时非镀膜区域,即留白区域202不需要覆盖保护材料,故能简化操作流程,从而提升制备效率。Further, specifically in this embodiment, the base material strip 210 is electroplated using brush plating. Since brush plating does not require a plating tank, the equipment is simple, the floor space is small, and the cost is low. Moreover, when brush plating is used, the non-coating area, that is, the blank area 202, does not need to be covered with protective material, so the operation process can be simplified, thereby improving the preparation efficiency.
需要指出的是,在其他实施例中,在进行化学镀之前,还可在活化区域201形成粘接层,该粘接层起过渡作用,与聚合物及金属材料之间均能够形成较强的结合力。示例的,粘接层可以包括聚氨酯系粘接剂。It should be pointed out that in other embodiments, before performing electroless plating, an adhesive layer can also be formed in the activation area 201. This adhesive layer serves as a transition and can form a strong bond with both polymer and metal materials. Binding force. For example, the adhesive layer may include a polyurethane adhesive.
如图4所示,由于金属层220只形成于活性区域201,即基材料带210的中部,留白区域202并不形成金属层220。因此,电镀时的边缘电流效应导致的穿孔或破损,将主要集中于基材料带210的中部与金属层220边缘对应的位置,而基材料带210的边缘将保持较好的完整性。基材料带210中部的缺陷相较于边缘的缺陷对基材料带210机械强度的影响较小,故基材料带210不易在走带过程中破损或断带。此外,由于边缘未受损的基材料带210能够承受更大的张
力,故在保证不断带的前提下,基材料带210的走带速度能够得到提升,从而还能够进一步提升复合集流体200的制备效率。As shown in FIG. 4 , since the metal layer 220 is only formed in the active area 201 , that is, in the middle of the base material strip 210 , the metal layer 220 is not formed in the blank area 202 . Therefore, the perforation or damage caused by the edge current effect during electroplating will be mainly concentrated in the middle of the base material strip 210 corresponding to the edge of the metal layer 220 , while the edge of the base material strip 210 will maintain good integrity. Defects in the middle of the base material tape 210 have less impact on the mechanical strength of the base material tape 210 than defects at the edges, so the base material tape 210 is less likely to be damaged or broken during the tape transport process. Furthermore, since the base material strip 210 has undamaged edges, it can withstand greater tension. Therefore, on the premise of ensuring continuous belting, the belt conveying speed of the base material belt 210 can be increased, thereby further improving the preparation efficiency of the composite current collector 200 .
步骤S140,切除金属层220沿宽度方向两侧的边缘部分或留白区域202,以制得复合集流体200。Step S140 , cut off the edge portions or blank areas 202 on both sides of the metal layer 220 along the width direction to prepare the composite current collector 200 .
由于留白区域202并不具备导电性能,故无法作为电极,需要在制备电极前进行切除。在进行切除操作时,可以仅将基材料带210对应留白区域202的部分切除,也可在切除留白区域202的同时切除部分金属层220。Since the blank area 202 does not have electrical conductivity, it cannot be used as an electrode and needs to be removed before preparing the electrode. During the cutting operation, only the portion of the base material strip 210 corresponding to the blank area 202 may be cut off, or part of the metal layer 220 may be cut off while cutting off the blank area 202 .
如图4及图13所示,具体在本实施例中,切除留白区域202时,切边组件341沿图示虚线进行裁切,故所切除的宽度大于留白区域202的宽度,从而可将金属层220沿宽度方向两侧的边缘部分切除。如此,在对留白区域202进行切除的过程中,金属层220边缘位置的损伤可随之切除,从而能够得到质量更佳的复合集流体200,并能够显著提升复合集流体200的良品率。As shown in Figures 4 and 13, specifically in this embodiment, when cutting off the blank area 202, the trimming component 341 cuts along the dotted line in the figure, so the width of the cutout is greater than the width of the blank area 202, so that The edge portions on both sides of the metal layer 220 along the width direction are cut off. In this way, during the process of cutting off the blank area 202 , the damage at the edge of the metal layer 220 can be cut away, so that a composite current collector 200 with better quality can be obtained, and the yield rate of the composite current collector 200 can be significantly improved.
在本实施例中,在上述步骤S130之后,还包括步骤:在金属层220的表面形成抗氧化层。抗氧化层可以是经过钝化处理后在金属层220上形成的钝化层,从而使得金属层220具备更好的抗氧化性能。具体的,可将复合集流体200进入学钝化池,并通过含铬或镍的溶液对金属层220进行表面钝化。In this embodiment, after the above-mentioned step S130, a step is further included: forming an anti-oxidation layer on the surface of the metal layer 220. The anti-oxidation layer may be a passivation layer formed on the metal layer 220 after passivation treatment, so that the metal layer 220 has better anti-oxidation performance. Specifically, the composite current collector 200 can be put into a chemical passivation pool, and the surface of the metal layer 220 can be passivated with a solution containing chromium or nickel.
在本实施例中,以连续走带的方式对基材料带210进行放卷,并以连续走带的方式对制得的复合集流体200进行收卷。如此,上述方法便可以实现复合集流体200卷对卷的连续制备,有助于提升效率。In this embodiment, the base material tape 210 is unrolled in a continuous tape conveying manner, and the prepared composite current collector 200 is rolled up in a continuous tape conveying manner. In this way, the above method can realize the continuous preparation of 200 roll-to-roll composite current collectors, which helps to improve efficiency.
收卷后的复合集流体200可以卷料形式存储,在使用时直接放卷即可。显然,在其他实施例中,收卷的步骤可以省略,而制得的复合集流体200则直接进入涂布或切片等下一道工序,以进行锂电池电极的制备。The rolled composite current collector 200 can be stored in the form of a roll and can be directly unrolled when used. Obviously, in other embodiments, the winding step can be omitted, and the prepared composite current collector 200 can directly enter the next process such as coating or slicing to prepare lithium battery electrodes.
下面将结合几种具体的负极集流体的制备过程,对上述复合集流体制备方
法进行说明:The following will combine several specific preparation processes of negative electrode current collectors to summarize the above composite current collector preparation methods. Method to explain:
1、1200mm宽幅的Cu/PET/Cu的负极集流体。1. 1200mm wide Cu/PET/Cu negative electrode current collector.
提供厚度为6μm,宽度为1750mm的聚对苯二甲酸乙二醇酯,即PET料带,PET料带的走带速度约为40m/min;Provide polyethylene terephthalate with a thickness of 6μm and a width of 1750mm, that is, PET tape. The running speed of the PET tape is about 40m/min;
先使用电晕处理的方式在PET料带的中间1300mm宽度范围内的区域进行粗化处理,电晕功率大致为360W至1200W;再通过喷墨打印的方式,在PET料带中间1300mm宽度范围内的粗化区域涂覆敏化活化液,敏化活化液为含有1g/L~2g/L的AgNO3的水溶液。敏化活化液涂覆完毕后,再经过双面紫外线照射进行表面活化,便可使PET料带中间1300mm宽度范围内的区域成为活性区域201;First use corona treatment to roughen the area within the width of 1300mm in the middle of the PET tape. The corona power is roughly 360W to 1200W. Then use inkjet printing to roughen the area within the width of 1300mm in the middle of the PET tape. The roughened area is coated with a sensitizing activation liquid, which is an aqueous solution containing 1g/L to 2g/L AgNO 3 . After the sensitization activation liquid is coated, the surface is activated through double-sided ultraviolet irradiation, so that the area within the width of 1300mm in the middle of the PET strip can become the active area 201;
将表面活化后的PET料带浸入金属化学镀液中进行化学镀,化学镀温度一般控制在35℃~53℃之间,金属化学镀液为含有硫酸铜10g/L~15g/L、酒石酸钾钠18g/L~24g/L、EDTA(乙二胺四乙酸)8g/L~12g/L、亚铁***0.02g/L~0.03g/L、甲醛2.5g/L~3.5g/L、氢氧化钠6g/L~7g/L及碳酸钠3g/L~6g/L及少量其它添加剂的水溶液。经过一定时间后,在PET料带的活性区域201得到含铜的金属膜221;Dip the surface-activated PET tape into a metal electroless plating solution for electroless plating. The electroless plating temperature is generally controlled between 35°C and 53°C. The metal electroless plating solution contains 10g/L to 15g/L copper sulfate and potassium tartrate. Sodium 18g/L~24g/L, EDTA (ethylenediaminetetraacetic acid) 8g/L~12g/L, potassium ferrocyanide 0.02g/L~0.03g/L, formaldehyde 2.5g/L~3.5g/L , aqueous solution of sodium hydroxide 6g/L~7g/L, sodium carbonate 3g/L~6g/L and a small amount of other additives. After a certain period of time, a copper-containing metal film 221 is obtained in the active area 201 of the PET strip;
对化学镀后的PET料带进行电刷镀铜,对金属膜221进行加厚,直至厚度达到700nm至2000nm。其中,刷镀铜的镀液为含有硫酸铜150g/L~250g/L、硫酸50g/L~70g/L和少量其它添加剂的水溶液。电刷镀铜时PET料带的走带速度30m/min~50m/min,故需要设置张力控制机构进行缓存及释放,以使各个工序的走带相匹配;The electroless plated PET strip is electroplated with copper, and the metal film 221 is thickened until the thickness reaches 700 nm to 2000 nm. Among them, the plating solution for brush copper plating is an aqueous solution containing 150g/L to 250g/L of copper sulfate, 50g/L to 70g/L of sulfuric acid and a small amount of other additives. When brush copper plating, the tape traveling speed of PET tape is 30m/min ~ 50m/min, so it is necessary to set up a tension control mechanism for buffering and release so that the tape traveling in each process can match;
电刷镀完成后,先采用去离子水对得到的金属层220进行清洗,再浸入含有铬酸盐或重铬酸盐的水溶液中进行钝化,最后用去离子水再次进行清洗并烘
干。接着,将PET料带宽度方向的两侧分别切除宽度275mm的材料,便可得到1200mm宽幅的负极集流体。After the brush plating is completed, the obtained metal layer 220 is first cleaned with deionized water, then immersed in an aqueous solution containing chromate or dichromate for passivation, and finally cleaned again with deionized water and dried. Dry. Then, cut off 275mm wide material from both sides of the PET strip in the width direction to obtain a 1200mm wide negative electrode current collector.
2、700mm宽幅的Cu/PET/Cu的负极集流体2. 700mm wide Cu/PET/Cu negative electrode current collector
提供厚度为4.5μm,宽度为1200mm的PET料带;Provide PET tape with a thickness of 4.5μm and a width of 1200mm;
先采用乙醇在除油清洗池内对PET料带进行除油处理并干燥,再通过凹版涂布的方式将含有硫酸80g/L~120g/L、铬酐100g/L~250g/L且温度在40℃~50℃之间的粗化液涂覆在PET料带的中间800mm宽度范围内的区域进行化学粗化,并在粗化后用40℃~50℃的去离子水进行清洗并热风烘干;再通过凹版涂布的方式在粗化后的区域涂覆敏化活化液,敏化活化液为含有氯化钯0.5g/L~1.5g/L、氯化亚锡30g/L~40g/L、浓盐酸260g/L~320ml/L的钯胶体溶液。经过活化后,再经过含硫酸35g/L~55g/L的水溶液进行清洗,便可使PET料带中间800mm宽度范围内的区域成为活性区域201;First use ethanol to degrease and dry the PET tape in a degreasing cleaning tank, and then use gravure coating to remove sulfuric acid from 80g/L to 120g/L and chromic anhydride from 100g/L to 250g/L at a temperature of 40 The roughening liquid between ℃ ~ 50 ℃ is applied to the middle 800mm width range of the PET strip for chemical roughening. After roughening, it is washed with deionized water at 40 ℃ ~ 50 ℃ and dried with hot air. ; Then apply a sensitizing activating liquid on the roughened area by gravure coating. The sensitizing activating liquid contains palladium chloride 0.5g/L~1.5g/L and stannous chloride 30g/L~40g/ L, palladium colloidal solution of concentrated hydrochloric acid 260g/L~320ml/L. After activation, and then cleaning with an aqueous solution containing 35g/L to 55g/L sulfuric acid, the area within the 800mm width range in the middle of the PET strip can become the active area 201;
将表面活化后的PET料带浸入金属化学镀液中进行化学镀镍,化学镀镍的温度一般控制在75℃~90℃之间,金属镀液为含有硫酸镍23g/L~30g/L、次磷酸钠25g/L~35g/L、苹果酸15g/L~23g/L、醋酸钠12g/L~24g/L和少量其它添加剂的pH为4.8~5.6的水溶液。进行化学镀镍时,PET料带的走带速度约为35m/min。化学镀镍后,将在活化区域201得到含镍的金属膜221;Dip the surface-activated PET strip into a metal electroless plating solution for electroless nickel plating. The temperature of electroless nickel plating is generally controlled between 75°C and 90°C. The metal plating solution contains 23g/L to 30g/L of nickel sulfate. An aqueous solution of sodium hypophosphite 25g/L~35g/L, malic acid 15g/L~23g/L, sodium acetate 12g/L~24g/L and a small amount of other additives with a pH of 4.8~5.6. When performing electroless nickel plating, the conveying speed of PET tape is approximately 35m/min. After electroless nickel plating, a nickel-containing metal film 221 will be obtained in the activation area 201;
PET料带在经过含硫酸35g/L~55g/L的水溶液清洗后,再次浸入金属化学镀液中进行化学镀铜,化学镀铜的温度一般控制在65℃~73℃之间,金属镀液为含有硫酸铜10g/L~15g/L,EDTA二钠盐38g/L~47g/L、甲醛3.5g/L~4.5ml/L、氢氧化钠2.6g/L~3.7g/L的pH为11.5~12.5的水溶液。进行化学镀铜时,PET料带的走带速度在30m/min~50m/min之间。化学镀铜后将在原含镍金属膜的表面再形成一层含铜金属膜;
After the PET tape is cleaned with an aqueous solution containing 35g/L ~ 55g/L sulfuric acid, it is then immersed in a metal electroless plating solution for electroless copper plating. The temperature of electroless copper plating is generally controlled between 65°C and 73°C. The metal plating solution The pH contains copper sulfate 10g/L~15g/L, EDTA disodium salt 38g/L~47g/L, formaldehyde 3.5g/L~4.5ml/L, and sodium hydroxide 2.6g/L~3.7g/L. 11.5~12.5 aqueous solution. When performing electroless copper plating, the conveying speed of PET tape is between 30m/min and 50m/min. After electroless copper plating, another layer of copper-containing metal film will be formed on the surface of the original nickel-containing metal film;
在将PET料带经过含硫酸35g/L~55g/L的水溶液进行清洗后,按照前述相同的方式进行电刷镀及钝化,便可在活性区域201形成预设厚度的金属层220。接着,将PET料带宽度方向的两侧分别切除宽度250mm的材料,便可得到700mm宽幅的负极集流体。After cleaning the PET strip with an aqueous solution containing 35g/L to 55g/L sulfuric acid, brush plating and passivation are performed in the same manner as described above to form a metal layer 220 with a predetermined thickness in the active area 201 . Then, cut off 250mm of material on both sides of the PET strip in the width direction to obtain a 700mm wide negative electrode current collector.
3、1100mm宽幅的Cu/PP/Cu的负极集流体3. 1100mm wide Cu/PP/Cu negative electrode current collector
提供厚度为8μm,宽度为1600mm的聚丙烯,即PP料带,PP料带的走带速度约为43m/min;Provide polypropylene with a thickness of 8μm and a width of 1600mm, that is, PP tape. The tape running speed of the PP tape is about 43m/min;
采用飞秒激光刻蚀处理的方式在PP料带的中间1200mm宽度范围内的区域进行表面粗化,再通过喷墨打印的方式在PP料带中间1200mm宽度范围内的粗化区域涂覆敏化活化液,敏化活化液为含有的硫酸铜20g/L~30g/L、明胶8g/L~12g/L、硼氢化钠6g/L~9g/L、正丁醇15g/L~25ml/L的铜胶体溶液。活化后再经过含有浓硫酸35g/L~55g/L的水溶液进行清洗,便可使PP料带中间1200mm宽度范围内的区域成为活性区域201;The surface is roughened in the middle 1200mm width of the PP tape using femtosecond laser etching, and then sensitized by inkjet printing on the roughened area within the 1200mm width in the middle of the PP tape. Activation solution, the sensitization activation solution contains copper sulfate 20g/L~30g/L, gelatin 8g/L~12g/L, sodium borohydride 6g/L~9g/L, n-butanol 15g/L~25ml/L copper colloid solution. After activation, it is cleaned with an aqueous solution containing 35g/L ~ 55g/L concentrated sulfuric acid, so that the area within the width of 1200mm in the middle of the PP material belt can become the active area 201;
采用与制备上述第1种负极集流体相同的方式进行化学镀、电刷镀及钝化,便可在活性区域201形成预设厚度的金属层220。接着,将PP料带宽度方向的两侧分别切除宽度250mm的材料,便可得到1100mm宽幅的负极集流体。The metal layer 220 with a predetermined thickness can be formed in the active area 201 by performing electroless plating, brush plating and passivation in the same manner as in preparing the first type of negative electrode current collector. Then, cut off 250mm wide material on both sides of the PP strip in the width direction to obtain a negative electrode current collector with a width of 1100mm.
经过实际检测,上述三种负极集流体的产品及加工参数如下:
After actual testing, the products and processing parameters of the above three negative electrode current collectors are as follows:
After actual testing, the products and processing parameters of the above three negative electrode current collectors are as follows:
通过上表可知,采用上述复合集流体制备方法所制备的三种负极集流体的方块电阻率均满足锂电池需求,且直通率达到95%~98%、良品率达到97%以上、制备速度可达到30m/min~50m/min。可见,上述复合集流体制备方法具有高良
品率、高效率的优势。It can be seen from the above table that the sheet resistivity of the three negative electrode current collectors prepared by the above composite current collector preparation method all meet the needs of lithium batteries, and the through rate reaches 95% to 98%, the yield rate reaches more than 97%, and the preparation speed can be Reach 30m/min~50m/min. It can be seen that the above composite current collector preparation method has high The advantages of high product yield and high efficiency.
如前所述,由于铝的化学性质特殊,故化学镀与电镀相结合的镀膜方式不适用于形成含铝的金属层220,即不适用于正极集流体的制备。As mentioned above, due to the special chemical properties of aluminum, the plating method that combines electroless plating and electroplating is not suitable for forming the metal layer 220 containing aluminum, that is, it is not suitable for preparing the positive electrode current collector.
为了解决这一问题,在另一个实施例中,上述步骤S130步骤包括:对基材料带210进行化学镀,以在活性区域201形成预设厚度的金属层220。与上一个实施例相比,省略了电镀的流程,故化学镀的时间需适当延长。而且,化学镀所使用的金属化学镀液的类型也存在区别。In order to solve this problem, in another embodiment, the above step S130 includes: performing electroless plating on the base material strip 210 to form a metal layer 220 with a predetermined thickness in the active area 201 . Compared with the previous embodiment, the electroplating process is omitted, so the electroless plating time needs to be appropriately extended. Moreover, there are also differences in the types of metal electroless plating solutions used for electroless plating.
具体的,金属化学镀液可以是熔融盐镀铝溶液等。经过较长时间的化学镀后,便可直接在活性区域201形成预设厚度的铝层、铝合金层或含铝的多层复合结构。下面将结合一种具体的正极集流体的制备过程,对上述复合集流体制备方法进行说明:Specifically, the metal electroless plating solution may be a molten salt aluminum plating solution, etc. After a long period of electroless plating, an aluminum layer, an aluminum alloy layer, or a multi-layer composite structure containing aluminum with a predetermined thickness can be directly formed in the active area 201 . The above composite current collector preparation method will be described below in conjunction with a specific preparation process of the positive electrode current collector:
提供厚度为6μm,宽度为1750mm的PET料带,PET料带的走带速度约为40m/min;Provide PET tape with a thickness of 6μm and a width of 1750mm. The running speed of the PET tape is about 40m/min;
先使用电晕处理的方式在PET料带的中间1300mm宽度范围内的区域进行粗化处理,电晕功率360W~1200W;再通过喷墨打印的方式在中间1300mm宽度范围内的粗化区域涂覆敏化活化液,敏化活化液为含有1g/L~2g/L的AgNO3的水溶液。敏化活化液涂覆完毕后,再经过双面紫外线照射进行表面活化,便可使PET料带中间1300mm宽度范围内的区域成为活性区域201;First use corona treatment to roughen the area within the middle 1300mm width of the PET tape, with a corona power of 360W ~ 1200W; then use inkjet printing to coat the roughened area within the middle 1300mm width. Sensitization activation liquid, the sensitization activation liquid is an aqueous solution containing 1g/L to 2g/L AgNO 3 . After the sensitization activation liquid is coated, the surface is activated through double-sided ultraviolet irradiation, so that the area within the width of 1300mm in the middle of the PET strip can become the active area 201;
将表面活化后的PET料带浸入金属化学镀溶液中进行化学镀铝,化学镀的温度一般控制在15℃~45℃之间,金属化学镀溶液为AlCl3-EMIC,化学镀时PET料带的走带速度同样约为40m/min。经过一定时间后,便可在PET料带的活性区域201得到预设厚度的含铝的金属层220;The surface-activated PET strip is immersed in a metal electroless plating solution for electroless aluminum plating. The temperature of electroless plating is generally controlled between 15°C and 45°C. The metal electroless plating solution is AlCl3-EMIC. During electroless plating, the temperature of the PET strip is The tape transport speed is also about 40m/min. After a certain period of time, the aluminum-containing metal layer 220 with a preset thickness can be obtained in the active area 201 of the PET strip;
将PET料带宽度方向的两侧分别切除宽度275mm的材料,便可得到
1200mm宽幅的Al/PET/Al的正极集流体。Cut off the material with a width of 275mm on both sides of the PET tape in the width direction, and you can get 1200mm wide Al/PET/Al cathode current collector.
上述复合集流体制备方法,通过选择性预处理在基材料带210表面的中部形成活性区域201,并在基材料带210沿宽度方向的两侧边缘形成留白区域202,留白区域202为未经过处理的区域,故基材料带210两侧的边缘不会被损伤。而且,在形成金属层220的过程中,也只是针对活性区域201进行操作,留白区域202并不形成金属层220。而在形成金属层220时对基材料带210所造成的穿孔等损伤,往往出现在金属层220的边缘位置。可见,制备过程中能够尽量减少对基材料带210边缘的损伤,从而保持基材料带210较高的机械强度。而且,金属层220边缘位置的损伤可后续切除。因此,上述复合集流体制备方法能够显著提升良品率。In the above composite current collector preparation method, an active area 201 is formed in the middle of the surface of the base material strip 210 through selective pretreatment, and a blank area 202 is formed on both sides of the base material strip 210 along the width direction. The blank area 202 is unused. After processing, the edges on both sides of the base material strip 210 will not be damaged. Moreover, in the process of forming the metal layer 220, the operation is only performed on the active area 201, and the metal layer 220 is not formed on the blank area 202. When the metal layer 220 is formed, damage such as perforations to the base material strip 210 often occurs at the edges of the metal layer 220 . It can be seen that the damage to the edge of the base material strip 210 can be minimized during the preparation process, thereby maintaining a high mechanical strength of the base material strip 210 . Moreover, the damage at the edge of the metal layer 220 can be subsequently removed. Therefore, the above composite current collector preparation method can significantly improve the yield rate.
与传统的金属箔材集流体相比,采用上述方法制备得到的复合集流体200还具有以下优点:采用聚合物材质的基材料带210作为支撑,减少了金属的使用,可减重40%~70%,提升了电池能量密度,在金属价格高涨的形势下有降成本潜力;并且,还可以提升复合集流体200的柔韧性和加工性能。最后,在异常工况下,如内短路、物理穿刺等情况下,复合集流体200可发生断路、从而提升电池的安全性能。Compared with traditional metal foil current collectors, the composite current collector 200 prepared by the above method also has the following advantages: the base material strip 210 of polymer material is used as a support, which reduces the use of metal and can reduce the weight by 40%~ 70%, which increases the energy density of the battery and has the potential to reduce costs in the face of rising metal prices; and it can also improve the flexibility and processing performance of the composite current collector 200. Finally, under abnormal operating conditions, such as internal short circuit, physical puncture, etc., the composite current collector 200 can be disconnected, thereby improving the safety performance of the battery.
本公开还提供一种复合集流体制备装置,该复合集流体制备装置能够执行上述复合集流体制备方法,从而制得如图1所示的复合集流体200。The present disclosure also provides a composite current collector preparation device, which can perform the above composite current collector preparation method, thereby preparing the composite current collector 200 as shown in FIG. 1 .
请一并参阅图5,本公开一个实施例中的复合集流体制备装置300包括放卷机构310、预处理机构320、镀膜机构330切边机构340。Please also refer to FIG. 5 . In one embodiment of the present disclosure, the composite current collector preparation device 300 includes an unwinding mechanism 310 , a pretreatment mechanism 320 , a coating mechanism 330 and a trimming mechanism 340 .
放卷机构310用于提供基材料带210;预处理机构320用于在基材料带210表面的中部形成活性区域201,并在基材料带210表面宽度方向的两侧边缘形成留白区域202,活性区域201及留白区域202呈条形并沿基材料带210的长度方
向延伸;镀膜机构330用于在活性区域201形成金属层220;切边机构340用于切除金属层220沿宽度方向两侧的边缘部分或留白区域202,以制得复合集流体200。The unwinding mechanism 310 is used to provide the base material strip 210; the pretreatment mechanism 320 is used to form an active area 201 in the middle of the surface of the base material strip 210, and to form a blank area 202 on both sides of the edge in the width direction of the surface of the base material strip 210, The active area 201 and the blank area 202 are strip-shaped and extend along the length of the base material strip 210. extending in the direction; the coating mechanism 330 is used to form the metal layer 220 in the active area 201; the trimming mechanism 340 is used to cut off the edge portions or blank areas 202 on both sides of the metal layer 220 along the width direction to prepare the composite current collector 200.
需要指出的是,放卷机构310、预处理机构320、镀膜机构330及切边机构340的功能分别与上述复合集流体制备方法的步骤S110~S140具体流程相对应,故在此将不再赘述。It should be pointed out that the functions of the unwinding mechanism 310, the pretreatment mechanism 320, the coating mechanism 330 and the trimming mechanism 340 respectively correspond to the specific processes of steps S110 to S140 of the above composite current collector preparation method, so they will not be described again here. .
在本实施例中,复合集流体制备装置300还包括收卷机构350。其中,放卷机构310能够连续放卷基材料带210;而收卷机构350能够连续收卷复合集流体200。预处理机构320及镀膜机构330设置于放卷机构310与收卷机构350之间。可见,复合集流体制备装置300能够实现复合集流体200卷对卷的连续生产,从而有助于提升效率。In this embodiment, the composite current collector preparation device 300 further includes a winding mechanism 350 . Among them, the unwinding mechanism 310 can continuously unwind the base material strip 210; and the winding mechanism 350 can continuously wind up the composite current collector 200. The pretreatment mechanism 320 and the coating mechanism 330 are arranged between the unwinding mechanism 310 and the rewinding mechanism 350 . It can be seen that the composite current collector preparation device 300 can realize the continuous roll-to-roll production of the composite current collector 200, thereby helping to improve efficiency.
而且,由于预处理机构320和镀膜机构330只对基材料带210的中部进行处理,而在基材料带210两侧的边缘位置保留有留白区域202,故能够保持基材料带210较高的机械强度,从而使得基材料带210在卷绕过程中能够承受更大的张力,不易断带,显著提升良品率。Moreover, since the pre-processing mechanism 320 and the coating mechanism 330 only process the middle part of the base material belt 210, and leave blank areas 202 at the edges on both sides of the base material belt 210, the base material belt 210 can be maintained at a high level. The mechanical strength enables the base material tape 210 to withstand greater tension during the winding process and is less likely to break, significantly improving the yield rate.
请一并参阅图6,具体在本实施例中,放卷机构310包括放卷辊311、第一接带装置312、第一纠偏装置313及第一张力调节装置314。Please also refer to FIG. 6 . Specifically, in this embodiment, the unwinding mechanism 310 includes an unwinding roller 311 , a first tape splicing device 312 , a first deviation correction device 313 and a first tension adjustment device 314 .
基材料带210可以料卷的形式存储于放卷辊311并由放卷轴311放卷,第一接带装置312能够保证基材料带210放卷的连续性。第一张力调节装置314一般由多个过辊构成,多个过辊之间的相对距离可调。在各个工序的走带速度出现波动时,多个过辊通过相互靠近或远离,能够实现对基材料带210的缓存或释放,从而维持基材料带210张力的稳定。此外,为了改变基材料带210的走带方向,放卷机构310一般还包括多个导向辊(图未标)。
The base material tape 210 can be stored in the form of a roll on the unwinding roller 311 and unrolled by the unwinding shaft 311. The first tape splicing device 312 can ensure the continuity of the unwinding of the base material tape 210. The first tension adjustment device 314 is generally composed of a plurality of rollers, and the relative distance between the plurality of rollers is adjustable. When the belt running speed of each process fluctuates, multiple rollers can cache or release the base material belt 210 by moving closer or farther away from each other, thereby maintaining the stability of the tension of the base material belt 210 . In addition, in order to change the running direction of the base material tape 210, the unwinding mechanism 310 generally also includes a plurality of guide rollers (not labeled in the figure).
收卷机构350的结构与放卷机构310的结构大致相同,仅走带方向存在区别,故在此不再赘述。此外,收卷机构350中还可设置切边组件341及边料收集组件342(见图4)。切边组件314能够将基材料带210中的留白区域202从复合集流体200上切除,边料收集组件342将切除得到的废料进行收集。切除留白区域202时,所切除的宽度大于留白区域202的宽度,从而可将金属层220边缘存在缺陷的部分一起切除,进而得到质量更佳的复合集流体200。The structure of the rewinding mechanism 350 is substantially the same as that of the unwinding mechanism 310, and only the tape running direction is different, so the details will not be described again here. In addition, the winding mechanism 350 can also be provided with an edge trimming assembly 341 and an edge material collection assembly 342 (see Figure 4). The trimming assembly 314 can cut off the blank area 202 in the base material strip 210 from the composite current collector 200 , and the trimming assembly 342 collects the cut-off waste. When the blank area 202 is cut off, the width of the cutout is larger than the width of the blank area 202 , so that the defective portions on the edge of the metal layer 220 can be cut off together, thereby obtaining a composite current collector 200 with better quality.
在本实施例中,预处理机构320包括粗化处理机构321及活化处理机构322。其中,粗化处理机构321用于对基材料带210表面的中部进行粗化处理,以形成微结构;活化处理机构322用于在基材料带210表面粗化处理后的区域涂覆敏化活化液,以形成活性区域201。In this embodiment, the pretreatment mechanism 320 includes a roughening treatment mechanism 321 and an activation treatment mechanism 322. Among them, the roughening treatment mechanism 321 is used to roughen the middle part of the surface of the base material strip 210 to form a microstructure; the activation treatment mechanism 322 is used to apply sensitization activation on the roughened area of the base material strip 210 surface. liquid to form the active area 201.
粗化处理机构321可采用物理粗化或化学粗化的方式对基材料带210表面进行粗化。譬如,请参阅图7,在一个实施例中,粗化处理机构321包括物理粗化组件3211以及位于物料粗化组件3211上游端及下游端的导辊3212。The roughening processing mechanism 321 can roughen the surface of the base material belt 210 by physical roughening or chemical roughening. For example, please refer to FIG. 7 . In one embodiment, the roughening processing mechanism 321 includes a physical roughening component 3211 and guide rollers 3212 located at the upstream and downstream ends of the material roughening component 3211 .
物理粗化组件3211一般设置有相对设置的两个,用于同时对基材料带210的两面进行粗化。物理粗化组件3211可以是激光发射器、紫外线发射器、等离子发射器及电晕组件等。放卷机构310放卷的基材料带210能够经过上游端的导辊3212的导向后进入物理粗化组件3211的工作范围,以对基材料带210表面的中部进行粗化,粗化完成后由下游端的导辊3212将基材料带210导出。The physical roughening components 3211 are generally provided with two opposite ones, which are used to roughen both sides of the base material strip 210 at the same time. The physical roughening component 3211 may be a laser emitter, an ultraviolet emitter, a plasma emitter, a corona component, etc. The base material strip 210 unrolled by the unwinding mechanism 310 can enter the working range of the physical roughening assembly 3211 after being guided by the guide roller 3212 at the upstream end to roughen the middle part of the surface of the base material strip 210. After the roughening is completed, the base material strip 210 is unrolled by the downstream end. The guide roller 3212 at the end guides the base material strip 210 out.
请一并参阅图8,在另一个实施例中,粗化处理机构321包括除油池3213、至少两个化学粗化涂布装置3214、第一烘干加热装置3215、第二张力调节装置3216及第一清洗池3217。Please refer to Figure 8 together. In another embodiment, the roughening treatment mechanism 321 includes an oil removal pool 3213, at least two chemical roughening coating devices 3214, a first drying and heating device 3215, and a second tension adjustment device 3216. and the first cleaning pool 3217.
化学粗化涂布装置3214可以采用凹版涂布、喷墨打印、挤压涂布、喷涂等方式进行化学粗化液的涂布,化学粗化液可采用含有双氧水、硫酸、铬酸、高
锰酸钾中的一种或多种水溶液。第一烘干加热装置3215加热方式可以是热风加热、红外加热、激光加热或它们的组合。The chemical roughening coating device 3214 can use gravure coating, inkjet printing, extrusion coating, spray coating, etc. to coat the chemical roughening liquid. The chemical roughening liquid can be made of hydrogen peroxide, sulfuric acid, chromic acid, high One or more aqueous solutions of potassium manganate. The heating method of the first drying heating device 3215 may be hot air heating, infrared heating, laser heating or a combination thereof.
此外,为了实现顺利走带,粗化处理机构321一般还设置有多个导向辊(图未标),以改变基材料带210的走带方向。而且,为了防止基材料带210将清洗剂带出,每个除油池3213及第一清洗池3217的输出端还设置有截液辊(图未标),第一清洗池3217中的清洗剂可以为去离子水。In addition, in order to achieve smooth belt conveyance, the roughening processing mechanism 321 is generally provided with a plurality of guide rollers (not labeled) to change the conveyor belt conveyor direction of the base material belt 210 . Moreover, in order to prevent the base material belt 210 from bringing out the cleaning agent, the output end of each degreasing pool 3213 and the first cleaning pool 3217 is also provided with a liquid catching roller (not labeled). The cleaning agent in the first cleaning pool 3217 It can be deionized water.
请一并参阅图9,具体在本实施例中,活化处理机构322包括至少两个活化液涂布装置3221、激活和烘干加热装置3222、第三张力调节装置3223、第二清洗池3224。Please refer to Figure 9 together. Specifically, in this embodiment, the activation treatment mechanism 322 includes at least two activation liquid coating devices 3221, an activation and drying heating device 3222, a third tension adjustment device 3223, and a second cleaning pool 3224.
活化液涂布装置3221可以采用凹版涂布、喷墨打印、挤压涂布、喷涂等方式涂覆活化敏化液,敏化活化液可以是包含有铜、锡、银、铂、钯、锰中的一种或多种离子或胶体的水溶液。激活和烘干加热装置3222进行激活方式可以是加热、紫外线照射,而加热方式可以是热风加热、红外加热、激光加热或它们的组合。此外,活化处理机构322也一般设置有多个导向辊(图未标),以改变基材料带210的走带方向。而且,每个第二清洗池3224的输出端也设置有截液辊(图未标),第二清洗池3224中的清洗剂可以为去离子水。The activation liquid coating device 3221 can apply the activation sensitizing liquid using gravure coating, inkjet printing, extrusion coating, spray coating, etc. The sensitizing activating liquid can contain copper, tin, silver, platinum, palladium, manganese An aqueous solution of one or more ions or colloids. The activation and drying heating device 3222 can be activated by heating, ultraviolet irradiation, and the heating method can be hot air heating, infrared heating, laser heating or a combination thereof. In addition, the activation treatment mechanism 322 is also generally provided with a plurality of guide rollers (not labeled) to change the direction of the base material belt 210 . Moreover, the output end of each second cleaning tank 3224 is also provided with a liquid-catching roller (not labeled), and the cleaning agent in the second cleaning tank 3224 can be deionized water.
请再次参阅图5,在本实施例中镀膜机构330包括化学镀机构331及电镀机构332。其中,化学镀机构331用于对基材料带210进行化学镀,以形成附着活性区域201的金属膜221;电镀机构332用于对经过化学镀的基材料带210进行电镀,以在金属膜221的表面形成预设厚度的金属层220。Please refer to FIG. 5 again. In this embodiment, the coating mechanism 330 includes an electroless plating mechanism 331 and an electroplating mechanism 332 . Among them, the electroless plating mechanism 331 is used to perform electroless plating on the base material strip 210 to form a metal film 221 attached to the active area 201; the electroplating mechanism 332 is used to perform electroplating on the electroless plated base material strip 210 to form a metal film 221 on the base material strip 210. A metal layer 220 with a predetermined thickness is formed on the surface.
需要指出的是,由于铝的化学性质比较活泼,容易在电镀过程中与氧气结合而快速氧化。因此,上述镀膜机构330一般只适用于负极集流体的制备,所制得的金属层220为铜层、铜合金层或含铜的多层复合结构。
It should be pointed out that due to the relatively active chemical properties of aluminum, it is easy to combine with oxygen and quickly oxidize during the electroplating process. Therefore, the above-mentioned coating mechanism 330 is generally only suitable for preparing the negative electrode current collector, and the produced metal layer 220 is a copper layer, a copper alloy layer, or a multi-layer composite structure containing copper.
请一并参阅图10,具体在本实施例中,化学镀机构331包括化学镀液池3311、设置于化学镀液池3311内的搅拌装置3312及控温装置3313、第四张力调节装置3314、第三清洗池3315、烘干装置3316及在线测厚装置3317。Please refer to Figure 10 together. Specifically, in this embodiment, the electroless plating mechanism 331 includes an electroless plating liquid pool 3311, a stirring device 3312 and a temperature control device 3313 disposed in the electroless plating liquid pool 3311, a fourth tension adjustment device 3314, The third cleaning tank 3315, the drying device 3316 and the online thickness measurement device 3317.
搅拌装置3312可以是桨式搅拌、超声搅拌或气流搅拌,在线测厚装置3317采用非接触式测厚,可以是激光测厚、X-ray测厚、β-ray测厚、涡电流或电阻值测厚。此外,为了实现顺利走带,化学镀机构331一般还设置有多个导向辊(图未标),以改变基材料带210的走带方向。而且,为了防止基材料带210将液体带出,每个化学镀液池3311及第三清洗池3315的输出端还设置有截液辊(图未标),第三清洗池3315中的清洗剂可以为去离子水。The stirring device 3312 can be paddle stirring, ultrasonic stirring or airflow stirring. The online thickness measuring device 3317 adopts non-contact thickness measurement, which can be laser thickness measurement, X-ray thickness measurement, β-ray thickness measurement, eddy current or resistance value. Measure thickness. In addition, in order to achieve smooth tape conveyance, the electroless plating mechanism 331 is generally provided with a plurality of guide rollers (not labeled) to change the tape conveyor direction of the base material tape 210 . Moreover, in order to prevent the base material belt 210 from bringing out the liquid, a liquid catching roller (not labeled) is also provided at the output end of each chemical plating bath 3311 and the third cleaning bath 3315. The cleaning agent in the third cleaning bath 3315 It can be deionized water.
本实施例中的电镀机构332采用的是电刷镀设备。请一并参阅图11,具体在本实施例中,电镀机构332包括阴极辊装置3321、阳极刷装置3322、电源控制装置3323、镀液供液和回收装置3324及第四清洗池3325、第二烘干装置3326及第二在线测厚装置3327。The electroplating mechanism 332 in this embodiment uses brush plating equipment. Please refer to Figure 11 together. Specifically, in this embodiment, the electroplating mechanism 332 includes a cathode roller device 3321, an anode brush device 3322, a power control device 3323, a plating solution supply and recovery device 3324, a fourth cleaning pool 3325, a second Drying device 3326 and second online thickness measurement device 3327.
阴极辊装置3321、阳极刷装置3322均为两个,用于分别对基材料带210的正反两面进行镀膜。阴极辊装置3321、阳极刷装置3322、电源控制装置3323通过电路进行连接控制。阴极辊装置3321包括不导电的阴极背辊及导电阴极辊;阳极刷装置3322的形状与阴极辊装置3321形状相匹配,包括阳极背辊及阳极包套。其中,阳极包套可以由多孔织物制成。镀液供液和回收装置3324包括镀液存储罐、搅拌组件、温控组件、镀液回收池、过滤装置、供液泵及喷嘴。第二烘干装置3326及第二在线测厚装置3327分别与上述烘干装置3316及在线测厚装置3317的结构及功能相同。There are two cathode roller devices 3321 and two anode brush devices 3322, which are used to coat the front and back sides of the base material strip 210 respectively. The cathode roller device 3321, the anode brush device 3322, and the power supply control device 3323 are connected and controlled through electric circuits. The cathode roller device 3321 includes a non-conductive cathode back roller and a conductive cathode roller; the shape of the anode brush device 3322 matches the shape of the cathode roller device 3321 and includes an anode back roller and an anode wrap. Among them, the anode cover can be made of porous fabric. The plating solution supply and recovery device 3324 includes a plating solution storage tank, a stirring component, a temperature control component, a plating solution recovery tank, a filter device, a solution supply pump and a nozzle. The second drying device 3326 and the second online thickness measuring device 3327 have the same structures and functions as the above-mentioned drying device 3316 and the online thickness measuring device 3317 respectively.
此外,为了实现顺利走带,电镀机构332一般还设置有多个导向辊(图未标),以改变基材料带210的走带方向。而且,为了防止基材料带210将液体
带出,每个第四清洗池3325的输出端还设置有截液辊(图未标),第四清洗池3325中的清洗剂可以为去离子水。In addition, in order to achieve smooth tape conveyance, the electroplating mechanism 332 is generally provided with a plurality of guide rollers (not labeled) to change the tape conveyor direction of the base material tape 210 . Furthermore, in order to prevent the base material belt 210 from absorbing the liquid Take out, the output end of each fourth cleaning pool 3325 is also provided with a liquid-collecting roller (not labeled), and the cleaning agent in the fourth cleaning pool 3325 can be deionized water.
化学镀机构331及电镀机构332均可以是现有技术中常用的化学镀设备及电镀设备,故在此不再对化学镀机构331及电镀机构332的具体结构及工作过程进行赘述。The electroless plating mechanism 331 and the electroplating mechanism 332 can both be electroless plating equipment and electroplating equipment commonly used in the prior art, so the specific structures and working processes of the electroless plating mechanism 331 and the electroplating mechanism 332 will not be described again.
化学镀能够顺利在非金属的基材料带210的表面形成较薄的金属膜221,从而对后续金属层220的成型提供基础。而且,相对于物理气相沉积,化学镀的环境较为温和,且对基材料带210表面的冲击较小。而对相较于化学镀,电镀工艺在金属层220成型时效率更高,且形成的金属层220更加致密,导电性也更佳。因此,镀膜机构330能够结合化学镀及电镀两种工艺的优势。Electroless plating can smoothly form a thin metal film 221 on the surface of the non-metallic base material strip 210, thereby providing a basis for the subsequent formation of the metal layer 220. Moreover, compared with physical vapor deposition, the environment of electroless plating is relatively mild, and the impact on the surface of the base material strip 210 is smaller. Compared with electroless plating, the electroplating process is more efficient when forming the metal layer 220, and the formed metal layer 220 is denser and has better conductivity. Therefore, the coating mechanism 330 can combine the advantages of both electroless plating and electroplating processes.
此外,相较于真空物理气相沉积设备,化学镀机构331与电镀机构332的成膜条件差异较小,从而方便连线成为整线的卷对卷生产线。基材料带210的料带可直接由化学镀机构331的输出端进入电镀机构332,期间可避免过长时间的缓存,从而有效地避免了空气中的水氧在基材料带210表面形成氧化薄膜,保证了最终产品的质量。In addition, compared with vacuum physical vapor deposition equipment, the film forming conditions of the electroless plating mechanism 331 and the electroplating mechanism 332 are less different, making it easier to connect them into a complete roll-to-roll production line. The material strip of the base material strip 210 can directly enter the electroplating mechanism 332 from the output end of the electroless plating mechanism 331. During this process, buffering for a long time can be avoided, thereby effectively preventing water and oxygen in the air from forming an oxide film on the surface of the base material strip 210. , ensuring the quality of the final product.
如前所述,由于铝的化学性质特殊,故化学镀与电镀相结合的镀膜机构330不适用于形成含铝的金属层220,即不适用于正极集流体的制备。As mentioned above, due to the special chemical properties of aluminum, the coating mechanism 330 that combines electroless plating and electroplating is not suitable for forming the metal layer 220 containing aluminum, that is, it is not suitable for preparing the positive electrode current collector.
为了解决这一问题,请参阅图12,本公开另一个实施例中的镀膜机构330能够对基材料带210进行化学镀,以在活性区域201形成预设厚度的金属层220。In order to solve this problem, please refer to FIG. 12 . The coating mechanism 330 in another embodiment of the present disclosure can perform electroless plating on the base material strip 210 to form a metal layer 220 with a predetermined thickness in the active area 201 .
与上一个实施例相比,镀膜机构330省略了电镀的流程,故适用于正极集流体的制备。镀膜机构330可直接采用现有技术中常用的化学镀设备,且在化学镀工艺所使用的金属化学镀液的类型相较于上一个实施例也存在区别。具体的,金属化学镀液可以是熔融盐镀铝溶液等。经过较长时间的化学镀后,镀膜
机构330便可直接在活性区域201形成预设厚度的铝层、铝合金层或含铝的多层复合结构。Compared with the previous embodiment, the coating mechanism 330 omits the electroplating process, so it is suitable for the preparation of positive electrode current collectors. The coating mechanism 330 can directly use electroless plating equipment commonly used in the prior art, and the type of metal electroless plating liquid used in the electroless plating process is also different from the previous embodiment. Specifically, the metal electroless plating solution may be a molten salt aluminum plating solution, etc. After a long period of electroless plating, the coating The mechanism 330 can directly form an aluminum layer, an aluminum alloy layer, or a multi-layer composite structure containing aluminum with a predetermined thickness in the active area 201 .
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。The technical features of the above embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, All should be considered to be within the scope of this manual.
以上所述实施例仅表达了本公开的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对公开专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本公开构思的前提下,还可以做出若干变形和改进,这些都属于本公开的保护范围。因此,本公开专利的保护范围应以所附权利要求为准。
The above-described embodiments only express several implementation modes of the present disclosure, and their descriptions are relatively specific and detailed, but should not be construed as limiting the scope of the disclosed patent. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present disclosure, and these all fall within the protection scope of the present disclosure. Therefore, the protection scope of the patent disclosed should be determined by the appended claims.
Claims (18)
- 一种复合集流体制备方法,包括步骤:A composite current collector preparation method, including the steps:提供基材料带;Provide base material tape;在所述基材料带表面的中部形成活性区域,并在所述基材料带沿宽度方向的两侧边缘形成留白区域,所述活性区域及所述留白区域均呈条形并沿所述基材料带的长度方向延伸;An active area is formed in the middle of the surface of the base material strip, and a blank area is formed on both sides of the base material strip along the width direction. The active area and the blank area are both strip-shaped and extend along the The lengthwise extension of the strip of base material;在所述活性区域形成金属层;forming a metal layer in the active area;切除所述金属层沿宽度方向两侧的边缘部分或所述留白区域,以制得复合集流体。The edge portions or the blank areas on both sides of the metal layer along the width direction are cut off to prepare a composite current collector.
- 根据权利要求1所述的复合集流体制备方法,其中,在所述基材料带表面的中部形成活性区域,并在所述基材料带沿宽度方向的两侧边缘形成留白区域的步骤包括:The composite current collector preparation method according to claim 1, wherein the step of forming an active area in the middle of the surface of the base material strip and forming a blank area on both sides of the base material strip along the width direction includes:对所述基材料带表面的中部进行粗化处理;Roughening the middle part of the surface of the base material strip;在粗化处理后的区域涂覆敏化活化液,以形成所述活性区域;Apply a sensitizing activation liquid to the roughened area to form the active area;其中,所述基材料带沿宽度方向的两侧边缘未经粗化处理且未涂覆敏化活化液的区域形成所述留白区域。Wherein, the areas on both sides of the base material strip along the width direction that have not been roughened and have not been coated with the sensitizing activating liquid form the blank area.
- 根据权利要求1或2所述的复合集流体制备方法,其中,对所述基材料带表面的中部进行粗化处理的步骤包括:对所述基材料带表面的多个条形区域进行粗化处理,所述条形区域位于所述基材料带表面的中部,且沿所述基材料带的宽度方向间隔设置;The composite current collector preparation method according to claim 1 or 2, wherein the step of roughening the middle part of the surface of the base material strip includes: roughening a plurality of strip areas on the surface of the base material strip Processing, the strip-shaped area is located in the middle of the surface of the base material strip and is spaced apart along the width direction of the base material strip;其中,在粗化处理后的所述条形区域涂覆敏化活化液以形成所述活性区域,相邻所述条形区域之间未经粗化处理且未涂覆敏化活化液的区域形成所述留白区域。 Wherein, the strip-shaped area after roughening treatment is coated with a sensitizing activation liquid to form the active area, and the area between the adjacent strip-shaped areas is not roughened and is not coated with the sensitizing activation liquid. Create the blank area.
- 根据权利要求1至3任一项所述的复合集流体制备方法,其中,所述复合集流体包括负极复合集流体,在所述活性区域形成金属层的步骤包括:The composite current collector preparation method according to any one of claims 1 to 3, wherein the composite current collector includes a negative electrode composite current collector, and the step of forming a metal layer in the active region includes:对所述基材料带进行化学镀,以形成附着于所述活性区域的金属膜;Electroless plating is performed on the base material strip to form a metal film attached to the active area;对经过化学镀的所述基材料带进行电镀,以在所述金属膜的表面形成预设厚度的所述金属层。The electroless plated base material strip is electroplated to form the metal layer with a predetermined thickness on the surface of the metal film.
- 根据权利要求1至4任一项所述的复合集流体制备方法,其中,采用电刷镀的方式对所述基材料带进行电镀。The composite current collector preparation method according to any one of claims 1 to 4, wherein the base material strip is electroplated by brush plating.
- 根据权利要求1至5任一项所述的复合集流体制备方法,其中,所述复合集流体包括正极复合集流体,在所述活性区域形成金属层的步骤包括:对所述基材料带进行化学镀,以在所述活性区域形成预设厚度的所述金属层。The method for preparing a composite current collector according to any one of claims 1 to 5, wherein the composite current collector includes a positive electrode composite current collector, and the step of forming a metal layer in the active region includes: subjecting the base material strip to Electroless plating to form the metal layer with a predetermined thickness in the active area.
- 根据权利要求1至6任一项所述的复合集流体制备方法,其中,在所述活性区域形成金属层的步骤之后,还包括步骤:在所述金属层的背离所述基材料带的表面形成抗氧化层。The composite current collector preparation method according to any one of claims 1 to 6, wherein, after the step of forming a metal layer in the active area, it further includes the step of: forming a surface of the metal layer away from the base material strip. Form an antioxidant layer.
- 根据权利要求1至7任一项所述的复合集流体制备方法,其中,以连续走带的方式对所述基材料带进行放卷;以连续走带的方式对制得的所述复合集流体进行收卷。The composite current collector preparation method according to any one of claims 1 to 7, wherein the base material tape is unrolled in a continuous tape conveying manner; and the prepared composite current collector is rolled in a continuous tape conveying manner. The fluid is rolled up.
- 一种复合集流体制备装置,包括:A composite current collector preparation device, including:放卷机构,用于提供基材料带;Unwinding mechanism for supplying strips of base material;预处理机构,用于在所述基材料带表面的中部形成活性区域,并在所述基材料带沿宽度方向的两侧边缘形成留白区域,所述活性区域及所述留白区域均呈条形并沿所述基材料带的长度方向延伸;A pretreatment mechanism is used to form an active area in the middle of the surface of the base material strip, and to form a blank area on both sides of the base material strip along the width direction. The active area and the blank area are both in the shape of Strip shape and extending along the length direction of the base material strip;镀膜机构,用于在所述活性区域形成金属层;A coating mechanism used to form a metal layer in the active area;切边机构,用于切除所述金属层沿宽度方向两侧的边缘部分或所述留白区 域,以制得复合集流体。Trimming mechanism, used to cut off the edge portions on both sides of the metal layer along the width direction or the blank area domain to prepare composite current collectors.
- 根据权利要求9所述的复合集流体制备装置,其中,所述放卷机构能够连续放卷所述基材料带,所述复合集流体制备装置还包括及收卷机构,所述收卷机构能够连续收卷所述复合集流体。The composite current collector preparation device according to claim 9, wherein the unwinding mechanism can continuously unwind the base material strip, the composite current collector preparation device further includes a winding mechanism, the winding mechanism can The composite current collector is continuously rolled up.
- 根据权利要求9或10所述的复合集流体制备装置,其中,所述预处理机构包括:The composite current collector preparation device according to claim 9 or 10, wherein the pretreatment mechanism includes:粗化处理机构,用于对所述基材料带表面的中部进行粗化处理;A roughening treatment mechanism used to roughen the middle part of the surface of the base material strip;活化处理机构,用于在粗化处理后的区域涂覆敏化活化液,以形成所述活性区域;An activation treatment mechanism is used to apply sensitizing activation liquid on the roughened area to form the active area;其中,所述基材料带沿宽度方向的两侧边缘未经粗化处理且未涂覆敏化活化液的区域形成所述留白区域。Wherein, the areas on both sides of the base material strip along the width direction that have not been roughened and have not been coated with the sensitizing activating liquid form the blank area.
- 根据权利要求9至11任一项所述的复合集流体制备装置,其中,所述预处理机构包括:The composite current collector preparation device according to any one of claims 9 to 11, wherein the pretreatment mechanism includes:粗化处理机构,用于对所述基材料带表面的多个条形区域进行粗化处理,所述条形区域位于所述基材料带表面的中部,且沿所述基材料带的宽度方向间隔设置;A roughening treatment mechanism is used to roughen multiple strip-shaped areas on the surface of the base material strip. The strip-shaped areas are located in the middle of the surface of the base material strip and along the width direction of the base material strip. Interval setting;活化处理机构,用于在粗化处理后的所述条形区域涂覆敏化活化液以形成所述活性区域;An activation treatment mechanism for applying sensitizing activation liquid to the strip-shaped area after roughening treatment to form the active area;其中,相邻所述条形区域之间未经粗化处理且未涂覆敏化活化液的区域形成所述留白区域。Wherein, the area between adjacent strip-shaped areas that has not been roughened and not coated with sensitizing activation liquid forms the blank area.
- 根据权利要求9至12任一项所述的复合集流体制备装置,其中,还包括收卷机构,所述收卷机构包括多段式收卷辊,所述多段式收卷辊包括多个相互连接的子辊,相邻的所述子辊之间设置有锁紧机构。 The composite current collector preparation device according to any one of claims 9 to 12, further comprising a winding mechanism, the winding mechanism includes a multi-section winding roller, the multi-section winding roller includes a plurality of interconnected sub-rollers, and a locking mechanism is provided between adjacent sub-rollers.
- 根据权利要求9至13任一项所述的复合集流体制备装置,其中,多个所述子辊可拆卸地相互连接,所述子辊的数量与所述条形区域的数量相同。The composite current collector preparation device according to any one of claims 9 to 13, wherein a plurality of the sub-rollers are detachably connected to each other, and the number of the sub-rollers is the same as the number of the strip areas.
- 根据权利要求9至14任一项所述的复合集流体制备装置,其中,所述复合集流体制备装置用于制备负极复合集流体,所述镀膜机构包括:The composite current collector preparation device according to any one of claims 9 to 14, wherein the composite current collector preparation device is used to prepare a negative electrode composite current collector, and the coating mechanism includes:化学镀机构,用于对所述基材料带进行化学镀,以形成附着于所述活性区域的金属膜;An electroless plating mechanism for performing electroless plating on the base material strip to form a metal film attached to the active area;电镀机构,用于对经过化学镀的所述基材料带进行电镀,以在所述金属膜的表面形成预设厚度的所述金属层。An electroplating mechanism is used for electroplating the electroless plated base material strip to form the metal layer with a predetermined thickness on the surface of the metal film.
- 根据权利要求9至15任一项所述的复合集流体制备装置,其中,所述电镀机构采用电刷镀的方式对所述基材料带进行电镀。The composite current collector preparation device according to any one of claims 9 to 15, wherein the electroplating mechanism uses brush plating to electroplat the base material strip.
- 根据权利要求9至16任一项所述的复合集流体制备装置,其中,所述复合集流体制备装置用于制备正极复合集流体,所述镀膜机构用于对所述基材料带进行化学镀,以在所述活性区域形成预设厚度的所述金属层。The composite current collector preparation device according to any one of claims 9 to 16, wherein the composite current collector preparation device is used to prepare a positive electrode composite current collector, and the coating mechanism is used to perform electroless plating on the base material strip. , to form the metal layer with a predetermined thickness in the active area.
- 根据权利要求9至17任一项所述的复合集流体制备装置,其中,还包括位于所述镀膜机构与所述切边机构之间的钝化机构,所述钝化机构用于在所述金属层背离所述基材料带的表面形成抗氧化层。 The composite current collector preparation device according to any one of claims 9 to 17, further comprising a passivation mechanism located between the coating mechanism and the trimming mechanism, the passivation mechanism being used to The surface of the metal layer facing away from the base material strip forms an antioxidant layer.
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