CN117535740A - Electrolytic copper foil, method for producing the same, and article produced therefrom - Google Patents
Electrolytic copper foil, method for producing the same, and article produced therefrom Download PDFInfo
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- CN117535740A CN117535740A CN202310913081.3A CN202310913081A CN117535740A CN 117535740 A CN117535740 A CN 117535740A CN 202310913081 A CN202310913081 A CN 202310913081A CN 117535740 A CN117535740 A CN 117535740A
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- copper foil
- electrolytic copper
- electrolytic
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- electrolytic solution
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 239000011889 copper foil Substances 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 12
- 230000003746 surface roughness Effects 0.000 claims abstract description 11
- 238000004070 electrodeposition Methods 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 229920006317 cationic polymer Polymers 0.000 claims description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 150000002118 epoxides Chemical class 0.000 claims description 7
- 125000005647 linker group Chemical group 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002210 silicon-based material Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000013480 data collection Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000000992 sputter etching Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- -1 accelerators Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- CHGIBPCWTKJVIX-UHFFFAOYSA-N C(C)NC(=S)NCC.C(C)NC(=S)NCC Chemical compound C(C)NC(=S)NCC.C(C)NC(=S)NCC CHGIBPCWTKJVIX-UHFFFAOYSA-N 0.000 description 1
- 208000032953 Device battery issue Diseases 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WIYCQLLGDNXIBA-UHFFFAOYSA-L disodium;3-(3-sulfonatopropyldisulfanyl)propane-1-sulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)CCCSSCCCS([O-])(=O)=O WIYCQLLGDNXIBA-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000009931 pascalization Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- LHUAYJZGTZYKSW-UHFFFAOYSA-M sodium;1-sulfanylpropane-1-sulfonate Chemical compound [Na+].CCC(S)S([O-])(=O)=O LHUAYJZGTZYKSW-UHFFFAOYSA-M 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Disclosed is an electrolytic copper foil characterized in that: the electrodeposited surface of the electrolytic copper foil has an average surface roughness (S) of 3.50 μm or less z ) The method comprises the steps of carrying out a first treatment on the surface of the After heat treatment at 200 ℃ for 2 hours, the electrolytic copper foil has a twin boundary ratio of 35% or less, or 3.50 μm ‑1 Or greater total grain boundary density; electrolytic copper foil is manufactured by electrodeposition in an electrolytic solution; and the electrolytic solution contains 0.01ppm to 25.0ppm of chloride ions and 0.01ppm to 75.0ppm of additives. Also disclosed are methods of making electrolytic copper foil and articles made therefrom. Articles include lithium ion batteries or electric double layer capacitorsThe negative electrode current collector of (c), resin-coated copper, copper-clad laminate, flexible copper-clad laminate, various types of printed circuit boards, and the like.
Description
Technical Field
The present invention relates to an electrolytic copper foil having an average surface roughness (S) of a deposit surface of 3.50 μm or less z ) Low twin ratio or high total grain boundary density, fine grains and high tensile strength. The invention also relates to a method of making the electrolytic copper foil and articles made therefrom.
Background
Currently, all electric vehicles are directed to improving cruising ability, and the main method is to increase the unit capacity of lithium ion battery cells. There are several ways to increase capacitance, and the simplest, low risk methods include two approaches: (1) Reducing the thickness of the copper foil of the negative electrode current collector, and (2) replacing the graphite-based material of the negative electrode with a silicon material. The benefit of replacing graphite with silicon is that the theoretical energy density of silicon materials is as high as 4200mAh/g, about 10 times the theoretical energy density of graphite-based materials.
However, when the first solution is used, i.e., reducing the thickness of the copper foil to increase the energy density, the copper foil must have high tensile strength in order to reduce the thickness while still being able to carry the negative electrode material and withstand processing without breaking. With respect to the second solution, although the theoretical energy density of the silicon material is 10 times that of graphite, the volume expansion and contraction of the silicon material is also greater than that of the graphite material due to intercalation of lithium ions during the charge and discharge process. When a silicon material is used as the negative electrode material, it is still necessary to use a copper foil having high tensile strength to suppress excessive expansion so as to avoid current collector breakage and battery failure. In order to improve battery life and capacity of an electric vehicle, whichever of these solutions is used to increase energy density of a battery, it is necessary to use an electrolytic copper foil having high tensile strength and thermal stability.
Taiwan patent publications TW 1696727B and TW 1707062B disclose a method for manufacturing a high-strength electrolytic copper foil, mainly using a high proportion of nano twin crystals to achieve the purpose of strengthening the copper foil. However, the current density applied during electroplating by both of these manufacturing methods is relatively low and it is difficult to perform industrial mass production. Accordingly, there is still a lack of commercial high strength copper foil in the market to solve the current problem of increasing the energy density of thin circuit boards and battery cells. Based on solving these problems in the industry, the present invention proposes a method for industrially mass-producing high-strength electrolytic copper foil.
Drawings
Fig. 1 shows a flowchart for manufacturing an electrolytic copper foil according to the present invention.
Detailed Description
All publications, patent applications, patents, and other references mentioned herein are expressly incorporated herein by reference in their entirety, unless otherwise indicated.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
All percentages, parts, ratios, etc. are by weight unless otherwise specified.
As used herein, the term "made of … …" is synonymous with "comprising. As used herein, the terms "comprise," "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing" or any other variation thereof are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The phrase "consisting of … …" excludes any unspecified element, step or component. If in a claim, such phrase will cause the claim to be closed, making it free of materials other than those described, except for impurities typically associated therewith. When the phrase "consisting of … …" appears in a clause of the body of the claim, not immediately preceding it, it is limited to only the elements illustrated in that clause; other elements are not excluded from the claims as a whole. The phrase "consisting essentially of … …" is used to define a composition, method, or apparatus that includes materials, steps, features, components, or elements in addition to those discussed literally, provided that such additional materials, steps, features, components, or elements are not materially affected one or more of the basic and novel characteristics of the claimed invention. The term "consisting essentially of … …" is an intermediate zone between "comprising" and "consisting of … …". The term "comprising" is intended to include embodiments encompassed by the terms "consisting essentially of … …" and "consisting of … …". Similarly, the term "consisting essentially of … …" is intended to include embodiments encompassed by the term "consisting of … …".
Where an equivalent, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, it is to be understood that all ranges are formed by any pairing of any upper limit or preferred value of the range with any lower limit or preferred value of the range, whether or not the range is separately disclosed. For example, when a range of "1 to 5" is recited, the recited range should be interpreted to include "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and other ranges. When numerical ranges are described herein, unless otherwise stated, the ranges are intended to include the endpoints thereof, and all integers and fractions within the range. When the term "about" is used to describe a range of values or endpoints, the present disclosure should be understood to include the referenced specific value or endpoint.
Furthermore, unless explicitly stated to the contrary, "or" means an inclusive "or" and not an exclusive "or". For example, condition a "or" B is satisfied by any one of the following: a is true (or present) and B is false (or absent), a is false (or absent) and B is true (or present), and both a and B are true (or present).
As used herein, the term "hydrocarbyl" refers to an organic compound having at least one carbon atom and at least one hydrogen atom, optionally substituted where indicated with one or more substituents; the term "alkyl" refers to a straight or branched chain saturated hydrocarbon having the indicated number of carbon atoms and having a 1-valent bond; such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the like. "alkylene" refers to an alkyl group having a divalent bond. "cycloalkyl" means a monovalent group having one or more saturated rings in which all ring members are carbon; examples include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; "Cycloalkylene" refers to cycloalkyl groups having a divalent bond. "aryl" means a monovalent aromatic monocyclic or fused ring group polycyclic ring system, and may include groups having aromatic rings fused to at least one cycloalkyl group; such as phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, and the like. "aralkenyl" refers to an aryl group having a divalent bond. The total number of carbon atoms in the substituent is indicated with the "Ci-Cj" prefix; for example, C1-C6 alkyl refers to methyl, ethyl and the various propyl, butyl, pentyl and hexyl isomers. The term "optionally substituted" is used interchangeably with the word "substituted or unsubstituted" or with the term "(unsubstituted). The expression "optionally substituted with 1 to 4 substituents" means that no substituents (i.e. unsubstituted) or 1, 2, 3 or 4 substituents (limited by the available number of bonds at the junction position) are present. Unless otherwise indicated, an optionally substituted group may have one substituent at each substitutable position of the group, and each substitution is independent of the other.
Embodiments of the invention include any of the embodiments described herein, can be combined in any manner, and the description of the variables in the embodiments relates not only to the composite of the invention, but also to the products made therefrom.
The present invention is described in detail below.
The invention provides an electrolytic copper foil, which is characterized in that: average surface roughness of electrodeposited surface of electrodeposited copper foil (S z ) 3.50 μm or less; after heat treatment at 200 ℃ for 2 hours, the electrolytic copper foil has a twin boundary ratio of 35% or less or has a grain size of 3.50 μm -1 Or greater total grain boundary density (total grain boundary density); electrolytic copper foil is produced by electrodeposition in an electrolytic solution; and the electrolytic solution includes chloride ions in the range of about 0.01ppm to about 25.0ppm and additives in the range of about 0.01ppm to about 75.0 ppm.
It is considered that one of the objects of the present invention is to provide a negative electrode current collector suitable for a lithium ion battery, which, after high-pressure processing, if the surface roughness of its deposition surface is excessively large, an electrolytic copper foil may react with the negative electrode, resulting in an interlayer interfaceAnd (5) cracking. The surface roughness used in the scope of the present specification and patent application is the roughness of the electrodeposited surface of the electrodeposited copper foil of the present invention measured using a laser scanning microscope, and "S" is used z "as a standard for comparison.
In one embodiment, the average surface roughness (S z ) 3.50 μm or less; or 3.25 μm or less; or 3.00 μm or less; or 2.75 μm or less.
In another embodiment, after heat treatment at 200℃for 2 hours, the electrodeposited surface of the electrodeposited copper foil has an average surface roughness (S z ) 3.50 μm or less; or 3.25 μm or less; or 3.00 μm or less; or 2.75 μm or less.
On the other hand, it is another object of the present invention to provide a thin and high-strength electrolytic copper foil to satisfy the current demand for fine circuit boards and to improve battery energy density. The higher the strength of the copper foil, the less likely it will deform and buckle. If two copper foils have the same tensile strength, a thicker copper foil will have a higher strength. Because the strength of the copper foil is calculated by the following relationship:
strength (kgf/mm) = [ tensile strength (kgf/mm) 2 )]x [ thickness (mm)]
If two copper foils have the same thickness, a copper foil having a higher tensile strength will have a higher strength. If the thickness of the copper foil is reduced, the tensile strength of the copper foil must be increased in order to maintain the strength of the copper foil.
In one embodiment, the electrolytic copper foil has a tensile strength of about 40kgf/mm at normal temperature 2 Or larger; or about 45kgf/mm 2 Or larger; or about 50kgf/mm 2 Or larger; or about 55kgf/mm 2 Or larger.
In another embodiment, the electrolytic copper foil has a tensile strength of about 35kgf/mm after heat treatment at 200℃for 2 hours 2 Or larger; or about 40kgf/mm 2 Or greater or about 45kgf/mm 2 Or larger; or about 50kgf/mm 2 Or larger.
In one embodiment, the electrolytic copper foil of the present invention has both high tensile strength and high thermal stability.
Electron Back Scattering Diffraction (EBSD) was used to analyze the microstructure of the electrodeposited copper foil. At room temperature, the ratio of twin grain boundaries of the electrolytic copper foil crystal is about 35% or less. Meanwhile, after heat treatment at 200 ℃ for 2 hours, the twin boundary ratio of the electrolytic copper foil was also about 35% or less. Further, the electrolytic copper foil crystals have an average grain size of about 1.50 μm or less, whether at room temperature or after heat treatment at 200 ℃ for 2 hours.
After heat treatment at 200℃for 2 hours, the electrolytic copper foil has a Total Grain Boundary Density (TGBD) of about 3.50 μm -1 Or larger. Meanwhile, after heat treatment at 200℃for 2 hours, the electrodeposited copper foil had a thickness of about 3.00. Mu.m -1 Or greater high angle grain boundary density (HGBD) and/or about 0.10 μm -1 Or a greater low angle grain boundary density (LGBD). In addition, after heat treatment at 200 ℃ for 2 hours, the ratio of the high angle grain boundary density (HGBD) to the low angle grain boundary density (LGBD) of the electrolytic copper foil is less than 30.
In one embodiment, the electrolytic copper foil has a twin boundary ratio of about 35% or less after heat treatment at 200 ℃ for 2 hours; or about 30% or less; or about 25% or less.
In one embodiment, the electrodeposited copper foil has an average grain size of about 1.50 μm or less after heat treatment at 200 ℃ for 2 hours; or about 1.25 μm or less; or about 1.00 μm or less.
In one embodiment, the electrodeposited copper foil has a total grain boundary density of about 3.50 μm after heat treatment at 200℃for 2 hours -1 Or larger; or about 4.50 μm -1 Or larger; or about 5.50 μm -1 Or larger.
In one embodiment, the electrodeposited copper foil has a high angle grain boundary density of about 3.00 μm after heat treatment at 200℃for 2 hours -1 Or larger; or about 4.00 μm -1 Or larger; or about 5.00 μm -1 Or larger.
In one embodiment, the electrodeposited copper foil has a low angle grain boundary density of about 0.10 μm after heat treatment at 200℃for 2 hours -1 Or larger; or about 0.20 μm -1 Or largerThe method comprises the steps of carrying out a first treatment on the surface of the Or about 0.30 μm -1 Or larger.
In one embodiment, after heat treatment at 200 ℃ for 2 hours, the ratio of the high angle grain boundary density (HGBD) to the low angle grain boundary density (LGBD) of the electrodeposited copper foil is less than 30; or less than 25; or less than 20.
Since the electrolytic copper foil of the present invention has high strength and heat stability, it is easy to produce a copper foil having an extremely thin thickness, i.e., a thickness of 20 μm or less. In one embodiment, the electrolytic copper foil has a thickness of about 2 μm to about 18 μm; or about 4 μm to about 15 μm; or about 6 μm to about 12 μm.
Another object of the present invention is to provide a method for manufacturing an electrolytic copper foil.
The method comprises the following steps:
i) Providing an electrolytic solution in an electrolytic cell;
ii) applying an electric current to the anode plate and the rotating cathode roll spaced apart from each other in the electrolytic solution;
iii) Electrodepositing copper on a rotating cathode roll; and is also provided with
iv) separating the electrolytic copper foil from the cathode roll;
wherein the electrolytic solution comprises:
copper sulfate in the range of about 120g/L to about 450g/L,
sulfuric acid in the range of about 30g/L to about 140 g/L.
Chloride ions in the range of about 0.01ppm to about 25.0ppm, and
additives in the range of about 0.01ppm to about 75.0 ppm.
Fig. 1 is a flow chart of a method according to the invention. Referring to fig. 1, the method includes first performing step S100: providing an electrolytic solution in an electrolytic cell; then, step S200 is performed: applying an electric current; step S300 is then performed: electrodepositing copper on a cathode roll; and finally, step S400: and separating the prepared copper foil. The control conditions for electrodeposition include: the temperature of the electrolytic solution and the current density of the applied current. The copper foil formed has two surfaces. In the manufacturing process, the surface of the contact roller is referred to as the "roller surface" of the copper foil; and the opposite side of the roll surface, i.e. the surface facing the electrolytic solution, is called "electrodeposition surface".
The method of the invention has a wide operating temperature range of the electrolytic solution. The temperature of the plating solution is typically between about 20 c and about 80 c, preferably between about 30 c and about 60 c.
The method of the present invention also has a wide current operating range. Electrodeposition may be at about 20A/dm 2 To about 80A/dm 2 Performed at an applied current density within a range. Especially when electrodeposited at 60A/dm 2 Or more, the productivity of the copper foil can be up to 16 μm/min or more, which meets the standards for industrial high-speed production.
In the method of the present invention, the electrolytic solution includes copper sulfate, sulfuric acid, chloride ions, and additives. Copper sulfate (copper ion source) and sulfuric acid in electrolytic solutions are commercially available from a variety of sources and can be used without additional purification.
In one embodiment, the copper sulfate is present in the electrolytic solution in an amount of about 120g/L to about 450g/L based on the total volume of the electrolytic solution; or about 180g/L to about 400g/L; or from about 240g/L to about 350g/L based on the total volume of the electrolytic solution.
In one embodiment, the amount of sulfuric acid in the electrolytic solution is from about 30g/L to about 140g/L based on the total volume of the electrolytic solution; or about 35g/L to about 130g/L g/L; or about 40g/L to about 120g/L.
The chloride ion source may be copper chloride or hydrochloric acid. These sources of chloride ions are commercially available and can be used without additional purification.
In one embodiment, the chloride ion content in the electrolytic solution is from about 0.01ppm to about 25.0ppm based on the total weight of the electrolytic solution; or about 0.05ppm to about 20.0ppm; or about 0.1ppm to about 15.0ppm; or from about 0.5ppm to about 10.0ppm based on the total weight of the electrolytic solution.
Additives suitable for use in the electrolytic solution include gelatin, cellulose, nitrogen-containing cationic polymers, or combinations thereof. The additives used are not particularly limited as long as the prepared electrolytic copper foil has a low twin ratio, fine grains and thermal stability. As described above, the proportion of twin grain boundaries is less than 35% and the average grain size is 1.50 μm or less, regardless of whether the electrolytic copper foil is treated at room temperature or 200 ℃ for 2 hours.
In one embodiment, the additive is a nitrogen-containing cationic polymer.
In another embodiment, the nitrogen-containing cationic polymer is the reaction product of a diamine represented by formula (I) and an epoxide represented by formula (II) in a 1:1 molar ratio,
wherein the method comprises the steps of
R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Each independently is H or C1-C3 alkyl;
R 7 is a divalent linking group comprising a C2-C8 alkylene, C5-C10 cycloalkylene, and optionally substituted with-OH;
a is a divalent linking group comprising a C2-C8 alkylene, C5-C10 cycloalkylene, C6-C20 arylene or C6-C20 arylene-C1-C10 alkylene group;
p, q and r are each independently integers from 0 to 10; and n is an integer from 1 to 2.
The amount of additive used in the electrolytic solution in the process of the invention will depend on the particular additive selected, the concentration of copper ions in the electrolytic solution, the concentration of sulfuric acid, and the applied current density. When the total amount of the additive is less than 75.0ppm, mass production operations are facilitated and the use of activated carbon and other filter materials is reduced. Thus, the method of the present invention has advantages of being beneficial for mass production and environmental protection.
In one embodiment, the additive is present in the electrolytic solution in an amount of about 0.01ppm to about 75.0ppm based on the total weight of the electrolytic solution; or about 0.5ppm to about 50.0ppm; or about 1ppm to about 25.0ppm.
In the method of the invention, the electrolytic solution may additionally comprise one or more other additives, such as accelerators, inhibitors or levelling agents. These other additives may be used in one or more combinations as the case may be. Other additives are typically present in small amounts (i.e., less than 100 ppm) so long as they do not interfere with the functional properties of the electrodeposited copper foil of the present invention.
The electrolytic copper foil prepared by the method of the present invention has fine and thermally stable crystal grains; meanwhile, the twin boundary ratio is low, and the method is particularly suitable for preparing copper-clad laminates and flexible copper-clad laminates of microcircuit boards and negative current collectors of lithium ion batteries or double-layer capacitors. The electrolytic copper foil of the present invention has fine grains and can provide an effect of miniaturizing line width and line spacing. As long as it is subjected to an appropriate surface treatment, a circuit having high density, thin line width, and thin line pitch can be formed. On the other hand, since the electrolytic copper foil of the present invention has high tensile strength and thermal stability, it is easy to produce a thin copper foil (thickness less than 20 μm). Meanwhile, it may be used as a negative electrode current collector in combination with a high-capacity silicon material due to its high strength, thereby increasing the capacity of a lithium ion battery or an electric double layer capacitor.
It is another object of the present invention to provide an article having an electrodeposited copper foil. In one embodiment, the article is a negative current collector of a lithium ion battery or an electric double layer capacitor, a Resin Coated Copper (RCC) copper-clad laminate, a flexible copper-clad laminate, a rigid printed circuit board, a flexible printed circuit board, or a rigid-flexible printed circuit board.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. Accordingly, the following examples should be taken as illustrative only and not limiting the disclosure in any way.
Examples
The abbreviation "E" stands for "example", and "CE" stands for "comparative example", and the numbers following thereof indicate examples of producing electrolytic copper foil. Both examples and comparative examples were prepared and tested in a similar manner.
Material
Gelatin: purchased from Taiwan division (Shang Jie Taiwan) (Singapore's Jellice Biotechnology Company Taiwan Branch (jelice Taiwan)) of jevelocin technology, inc.
DETU: diethylthiourea (1, 3-diethyl-2-thiourea), available from alfa elsa corporation (Alfa Aesar Company).
SPS: sodium polydithio-dipropyl sulfonate (bis (sodium sulfopropyl) disulfide), available from the company HOPAX, inc.
PEG: polyethylene glycol (polyethylene glycol), M w : about 1000, available from alfa elsa.
MPS: sodium mercapto-1-propanesulfonate (sodium 3-mercapto-1-propanesulfonate), available from poly and International Co., ltd.
HEC: hydroxyethyl cellulose (hydroxyethyl cellulose), available from Daicel company.
NCP-A: nitrogen-containing cationic polymers available from DuPont electronics (DuPont Electronics) under the trade name MICROFILL TM The diamine represented by formula (I) and the epoxide represented by formula (II) are derived in a ratio of 1:1 molar, the reaction product of the ratio, wherein R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Are all hydrogen atoms H; p, q and r are all 0, A is C6 alkylene; and R is 7 Is C4 alkylene, M w : about 9000 or greater.
NCP-B: nitrogen-containing cationic polymers available from DuPont electronics under the trade designation MICROFILL TM The diamine represented by formula (I) and the epoxide represented by formula (II) are derived in a ratio of 1:1 molar. Reaction product of ratio, wherein R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Are all hydrogen atoms H; p, q and r are all 0, A is C6 alkylene; and R is 7 Is C6 alkylene, M w : about 3000 or less.
NCP-C: nitrogen-containing cationic polymers available from DuPont electronics (DuPont Electronics Company) under the trade name MICROFILL TM The diamine represented by formula (I) and the epoxide represented by formula (II) are derived in a ratio of 1:1 molar, the reaction product of the ratio, wherein R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Are all hydrogen atoms H; p, q and r are all 0, A is C6 alkylene; and R is 7 Is C8 cycloalkylene, M w : about 3000 or less.
NCP-D: nitrogen-containing cationic polymers available from DuPont electronics under the trade designation MICROFILL TM The diamine represented by formula (I) and the epoxide represented by formula (II) are derived in a ratio of 1:1 molar, the reaction product of the ratio, wherein R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Are all hydrogen atoms H; p, q and r are all 0; a is C6 alkylene; and R is 7 Is C4 alkylene, M w : about 3000 or less.
Copper sulfate (CuSO) 4 ) Purchased from taiwan rodoor haas electronic materials company (Taiwan Rohm and Haas Electronic Materials Company).
Sulfuric acid (H) 2 SO 4 ) Purchased from square company (Fangqiang Company).
Hydrochloric acid (HCl), purchased from friends and trade company (Youhe Trading Company).
Examples 1 to 20 and comparative examples 1 to 7
Table 1 shows copper sulfate, sulfuric acid, chloride ions and specific additives used to prepare the electrolytic solution.
For a rotating cell, the cathode roll is a titanium wheel and the anode is an insoluble anode (dimensionally stable anode, irO 2 Ti) and a DC power source is used to apply a current between the cathode and anode in the electrolytic solution. As shown in Table 1, 20-80A/dm was used 2 Is used for the current density of the battery. An electrolytic copper foil having a thickness in the range of 7-11 μm was directly formed on the surface of the titanium wheel using an electrolytic solution temperature of 40℃and a cathode rotation speed of 400 rpm. After the plating was completed, the electrolytic copper foil was removed from the titanium wheel, and the sample was analyzed. The results are shown in tables 2 and 3.
Analysis method
Evaluation of tensile Strength and elongation
Samples were made and tested according to the method of IPC-TM-650.2.4.18B. The samples were baked at 200 ℃ for 2 hours and then tested for tensile strength and elongation.
z Evaluation of average surface roughness (S)
Five regions of the copper foil sample were inspected using a laser scanning microscope (manufactured by Olympus, inc., model: OLS-5000) having a lens of 100 times magnification and no optical filter. According to the ISO25178 method, the roughness of the region is measured in each region, and the measured data is averaged. S is S z Is defined as the difference between the maximum peak height value and the maximum valley depth value in the measurement region.
Measurement of twin grain boundary ratio
EBSD samples were first polished and prepared by ion milling cross-section polisher, placed in SEM (JEOL-IT 800 SHL) cavity with 50 degrees pre-tilt holder, and then stage tilted 20 degrees. The acceleration voltage was set to 15-20kV using the high current mode. EBSD data is collected by Oxford Symmetric EBSD detector. The EBSD data collection parameters were set as follows: magnification was 3000x and acquisition step size was 0.1 μm.
AZTECCrystal software was used to analyze the EBSD data and output as BandContrast+ special grain boundary plot. The special grain boundary diagram parameters were set as follows: the minimum angle is 10 °, the copper phase, the crystal axis/angle is <111>/60 °, and the angular deviation is 1 °. Twin grain boundaries and grain boundary ratios are provided in the auto output graphs.
Average grain size measurement
EBSD samples were first prepared by polishing with an ion milling cross-section polisher, placed into an SEM (JEOL-IT 800 SHL) cavity with a 50 degree pre-tilt holder, and then tilted 20 degrees. The acceleration voltage was set to 15-20kV using the high current mode. EBSD data is collected by Oxford Symmetric EBSD detector. The EBSD data collection parameters were set as follows: magnification was 3000x and the collection step size was 0.1 μm.
For grain size analysis, EBSD data was loaded into AZtecCrystal software, the micro grain effect (< 0.5 μm) was removed, and the special boundaries in the twin boundaries (copper phase, <111>60 °) were ignored. The software automatically outputs grain size (equivalent circle diameter, ECD) information and distribution.
Total grain boundary density measurement
EBSD samples were first prepared by polishing with an ion milling cross-section polisher, placed into an SEM (JEOL-IT 800 SHL) cavity with a 50 degree pre-tilt holder, and then tilted 20 degrees. The acceleration voltage was set to 15-20kV using the high current mode. EBSD data is collected by Oxford Symmetric EBSD detector. The EBSD data collection parameters were set as follows: magnification was 3000x and the collection step size was 0.1 μm.
EBSD data was entered into the AZtecCrystal software version 3.0 and the area to be analyzed was selected. For grain boundary analysis, low angle grain boundaries (LGBD) angles were defined as 5 degrees to 15 degrees, and high angle grain boundaries (HGBD) were defined as greater than 15 degrees. The total length of the low angle grain boundaries and the total length of the high angle grain boundaries are obtained and divided by the area of the analysis zone to obtain the corresponding low angle grain boundary density or high angle grain boundary density. Then, the obtained low angle grain boundary density and high angle grain boundary density are added to obtain the Total Grain Boundary Density (TGBD) of the sample.
As can be seen from the data in tables 1 and 2, when the electrolytic solution used contained about 0.01ppm to about 25.0ppm of chloride ions and about 0.01ppm to about 75.0ppm of additives, the copper foils produced from E1 to E20 all had an average surface roughness of the precipitation planes of 3.50 μm or less (see table 2), and a twin boundary ratio of 35% or less (shown in table 2). Furthermore, the data in table 2 also show that the twin boundary ratio of these copper foils was also 35% or less after heat treatment at 200 ℃ for 2 hours.
The EBSD analysis photographs of example E7 and comparative example CE1 show that their microstructures are very different. The proportion of twin grain boundaries in the copper foil of E7 is 20.2%; the proportion of twin boundaries in CE1 was 63.4%. Furthermore, the difference in average grain size between the two was also quite different, the former was 0.78 μm and the latter was 3.40 μm.
TABLE 1
TABLE 2
TABLE 3 Table 3
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Referring to the data in Table 2 and comparing the tensile strengths of the copper foils of E1 to E20 and CE1 to CE7, all the copper foils had 40kg/mm before heating 2 Or greater tensile strength. However, after 2 hours of heat treatment at 200 ℃, the strength loss of the E1-E20 copper foil is small, and almost all examples maintain the tensile strength at 40kg/mm 2 Above. In contrast, the tensile strength of the copper foil was significantly reduced, and all comparative examples were reduced to 40kg/mm 2 Below. For example, although CE1, CE2 and CE5 all had a tensile strength exceeding 50kg/mm before heating 2 However, after heat treatment, the tensile strength of these copper foils was significantly reduced to 30kg/mm 2 Below, they are indicated to have no good strength and thermal stability. Therefore, they are not suitable for the needs of lithium battery negative electrode current collectors and thin circuit printed circuit boards.
As can be seen from Table 3, the copper foil produced from E1E 20 had a thickness of 3.50 μm after heat treatment at 200℃for 2 hours -1 Or greater, total Grain Boundary Density (TGBD), 3.00 μm -1 Or greater, and 0.10 μm -1 Or a greater low angle grain boundary density (LGBD). Meanwhile, the ratio of the high angle grain boundary density to the low angle grain boundary density (HGBD/LGBD) of the electrolytic copper foil is less than 30.
The EBSD analysis photographs of the copper foils of example E7 and comparative example CE1 show that the microstructures of both are very different. E7 has a total grain boundary density of 4.36. Mu.m -1 High angle grain boundary density of 4.13 μm -1 And a low-angle grain boundary density of 0.23 μm -1 . CE1 had a total grain boundary density of 1.26. Mu.m -1 High angle grain boundary density of 1.24 μm -1 And a low-angle grain boundary density of 0.02 μm -1 。
According to the method of the present invention, the chloride ion content is controlled to be between 0.01ppm and 25.0ppm, and 0.01ppm to 75.0ppm of an additive is added to the electrolytic solution while using a high current density (20 to 80A/dm 2 ) An electrolytic copper foil having low surface roughness, low twin boundary ratio, high total grain boundary density, high strength and thermal stability can be obtained. In addition, the electrolytic copper foil of the present invention is particularly suitable for a negative electrode current collector of a lithium ion battery or an electric double layer capacitor, and a copper-clad laminate for a printed circuit board having fine wires.
Claims (18)
1. An electrolytic copper foil, wherein:
average surface roughness of electrodeposited surface of the electrolytic copper foil (S z ) 3.50 μm or less;
after heat treatment at 200 ℃ for 2 hours, the electrolytic copper foil has: (i) A twin boundary ratio of 35% or less, or (ii) 3.50 μm -1 Or greater total grain boundary density; and is also provided with
The electrolytic copper foil is produced by electrodeposition in an electrolytic solution, wherein the electrolytic solution comprises:
chloride ions in the range of 0.01ppm to 25.0ppm; and
additives in the range of 0.01ppm to 75.0 ppm.
2. The electrolytic copper foil according to claim 1, wherein the electrolytic copper foil has an average grain size of 1.50 μm or less after heat treatment at 200 ℃ for 2 hours.
3. The electrolytic copper foil according to claim 1, wherein the electrolytic copper foil has a thickness of 3.00 μm after heat treatment at 200℃for 2 hours -1 Or greater, high angle grain boundary density, 0.10 μm -1 Or a greater low angle grain boundary density or both.
4. The electrolytic copper foil according to claim 1, wherein a ratio of the high-angle grain boundary density to the low-angle grain boundary density of the electrolytic copper foil after heat treatment at 200 ℃ for 2 hours is less than 30.
5. The electrolytic copper foil according to claim 1, wherein the tensile strength of the electrolytic copper foil after heat treatment at 200 ℃ for 2 hours is 35kg/mm 2 Or larger.
6. The electrolytic copper foil according to claim 1, wherein the electrolytic copper foil has a thickness of 20 μm or less.
7. The electrolytic copper foil according to claim 1, wherein the additive in the electrolytic solution comprises gelatin, cellulose, a nitrogen-containing cationic polymer, or a combination thereof.
8. The electrolytic copper foil according to claim 7, wherein the additive is a nitrogen-containing cationic polymer.
9. The electrolytic copper foil according to claim 8, wherein the nitrogen-containing cationic polymer is a reaction product of a diamine represented by the formula (I) and an epoxide represented by the formula (II) in a molar ratio of 1:1,
wherein:
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently is H or C1-C3 alkyl;
R 7 is a divalent linking group comprising a C2-C8 alkylene, C5-C10 cycloalkylene, and optionally substituted with-OH;
a is a divalent linking group comprising a C2-C8 alkylene, C5-C10 cycloalkylene, C6-C20 arylene or C6-C20 arylene-C1-C10 alkylene group;
p, q and r are each independently integers from 0 to 10; and is also provided with
n is an integer from 1 to 2.
10. The electrolytic copper foil according to claim 1, wherein the electrolytic solution further comprises copper sulfate in the range of 120g/L to 450g/L and sulfuric acid in the range of 30g/L to 140 g/L.
11. The electrolytic copper foil according to claim 1, wherein the electrodeposition is performed at 20A/dm 2 To 80A/dm 2 And at a current density within a range.
12. The electrolytic copper foil according to claim 1, wherein the electrodeposition is performed at an electrolytic solution temperature in the range of 30 ℃ to 60 ℃.
13. A method for manufacturing the electrolytic copper foil according to claim 1, comprising:
i) Providing an electrolytic solution in an electrolytic cell;
ii) applying an electric current to the anode plate and the rotating cathode roll spaced apart from each other in the electrolytic solution;
iii) Electrodepositing copper on the rotating cathode roll; and is also provided with
iv) separating the electrolytic copper foil from the cathode roll, wherein the electrolytic solution comprises:
copper sulfate in the range of 120g/L to 450g/L;
sulfuric acid in the range of 30g/L to 140g/L;
chloride ions in the range of 0.01ppm to 25.0ppm; and is also provided with
Additives in the range of 0.01ppm to 75.0 ppm.
14. The method of claim 13, wherein the current density at which current is applied is 20A/dm 2 To 80A/dm 2 Within the range.
15. The method of claim 13, wherein the temperature of the electrolytic solution is in the range of 30 ℃ to 60 ℃.
16. The method of claim 13, wherein the additive comprises gelatin, cellulose, a nitrogen-containing cationic polymer, or a combination thereof.
17. The method according to claim 16, wherein the additive is a nitrogen-containing cationic polymer which is a reaction product of a diamine represented by formula (I) and an epoxide represented by formula (II) in a molar ratio of 1:1,
wherein:
R 1 、R 2 、R 3 、R 4 、R 5 and R is 6 Each independently is H or C1-C3 alkyl;
R 7 is a divalent linking group comprising a C2-C8 alkylene, C5-C10 cycloalkylene, and optionally substituted with-OH;
a is a divalent linking group comprising a C2-C8 alkylene, C5-C10 cycloalkylene, C6-C20 arylene or C6-C20 arylene-C1-C10 alkylene group;
p, q and r are each independently integers from 0 to 10; and is also provided with
n is an integer from 1 to 2.
18. An article comprising the electrolytic copper foil of claim 1, wherein the article is a negative electrode current collector, a copper-clad foil, a copper-clad laminate, a flexible copper-clad laminate, a rigid printed circuit board, a flexible printed circuit board, or a rigid-flexible printed circuit board.
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