CN117512711A - High-elongation ultrathin electronic copper foil and preparation method and application thereof - Google Patents
High-elongation ultrathin electronic copper foil and preparation method and application thereof Download PDFInfo
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- CN117512711A CN117512711A CN202311737233.5A CN202311737233A CN117512711A CN 117512711 A CN117512711 A CN 117512711A CN 202311737233 A CN202311737233 A CN 202311737233A CN 117512711 A CN117512711 A CN 117512711A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000011889 copper foil Substances 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 77
- 230000000996 additive effect Effects 0.000 claims abstract description 69
- 239000011888 foil Substances 0.000 claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 56
- 239000003792 electrolyte Substances 0.000 claims description 35
- -1 polydithio-dipropyl Polymers 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 25
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 22
- 229910052708 sodium Inorganic materials 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 22
- 230000003064 anti-oxidating effect Effects 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 239000002639 bone cement Substances 0.000 claims description 14
- 238000009713 electroplating Methods 0.000 claims description 14
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 14
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 12
- 150000002191 fatty alcohols Chemical class 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical class OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- KQESUUZXLBJROK-UHFFFAOYSA-M sodium;3-(1,1,3-trioxo-1,2-benzothiazol-2-yl)propane-1-sulfonate Chemical compound [Na+].C1=CC=C2S(=O)(=O)N(CCCS(=O)(=O)[O-])C(=O)C2=C1 KQESUUZXLBJROK-UHFFFAOYSA-M 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- 230000002265 prevention Effects 0.000 abstract description 9
- 238000010301 surface-oxidation reaction Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 239000004353 Polyethylene glycol 8000 Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 229940085678 polyethylene glycol 8000 Drugs 0.000 description 2
- 235000019446 polyethylene glycol 8000 Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RGBLSOOLFKMJGA-UHFFFAOYSA-N [Na].C(=O)=CCC Chemical compound [Na].C(=O)=CCC RGBLSOOLFKMJGA-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 229940113125 polyethylene glycol 3000 Drugs 0.000 description 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 1
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The embodiment of the invention relates to the technical field of manufacturing of electronic copper foil for lithium batteries, and particularly discloses a high-extension ultrathin electronic copper foil, a preparation method and application thereof, wherein the high-extension ultrathin electronic copper foil provided by the embodiment of the invention is manufactured through a raw foil additive process and a copper foil surface oxidation prevention process, and the tensile strength of the prepared high-extension ultrathin electronic copper foil is more than 30kgf/cm 2 The roughness is less than 2.0 mu m, the elongation is more than 15.0%, the mechanical property is better, and the problem that the elongation is lower in the ultrathin electronic copper foil produced by the existing copper foil production enterprises is solved. Moreover, the preparation method of the high-extension ultrathin electronic copper foil provided by the embodiment of the invention is simple, meanwhile, the method can continuously and stably produce, the system is easy to adjust, the foil manufacturing yield is high, and the market prospect is wide.
Description
Technical Field
The embodiment of the invention belongs to the technical field of manufacturing of electronic copper foil for lithium batteries, and particularly relates to a high-extension ultrathin electronic copper foil, and a preparation method and application thereof.
Background
Copper foil has good conductivity and is widely applied to the electronic field, such as circuit boards, electronic components, electromagnetic shielding and the like. The lithium electric copper foil is used as a key material for influencing the quality capability density of the lithium battery, and is the first choice of a negative electrode current collector and a negative electrode material carrier of the lithium ion battery due to the characteristics of light texture, high conductive efficiency, outstanding cost advantage and the like. In recent years, as lithium batteries have been increased in capacity, thickness, density, and speed, the quality and performance requirements of lithium copper foil have been increasing. Wherein, the elongation is used as the plastic performance index of the copper foil and is the ratio of the total deformation of the gauge length after the tensile fracture of the test sample to the original gauge length. The lithium electric copper foil needs to have better mechanical property as a negative current collector, and the tensile strength and the elongation rate of the lithium electric copper foil need to meet certain requirements. The high elongation copper foil has excellent fracture resistance in repeated cycles of lithium ion charge and discharge, so that it can be safely and efficiently operated in a high energy density battery.
At present, extremely thin (less than or equal to 6 mu m) copper foil is used in power lithium batteries, and products with normal-temperature tensile strength of 300-350MPa mainly and elongation of more than or equal to 4% can be provided in the market generally. The thinner the copper foil is, the lower the elongation is, and the lower the elongation can cause the frequent occurrence of wrinkling and belt breakage phenomena of the lithium ion battery under the action of alternating stress in the electrochemical cycle process, so that the production cost is increased, and meanwhile, the battery core enterprises face larger quality risks.
However, the elongation of the extremely thin (less than or equal to 6 μm) electronic copper foil produced at home at present is generally lower than 15%, which cannot meet the demands of customers for higher elongation copper foils. In order to fully exert the function of the copper foil in the battery manufacturing, the improvement of the elongation of the copper foil is a current problem to be solved.
Thus, the prior art solutions described above have the following drawbacks: in the prior art, the elongation rate of extremely thin (less than or equal to 6 mu m) electronic copper foil produced by most copper foil production enterprises is generally lower than 15%, and the low elongation rate can cause frequent wrinkling and belt breakage of the lithium ion battery in the electrochemical cycle process, so that the requirements of customers cannot be met.
Disclosure of Invention
The embodiment of the invention aims to provide a high-elongation ultrathin electronic copper foil, which solves the problems that the elongation rate of the ultrathin electronic copper foil produced by the existing copper foil production enterprises is generally lower than 15% and the elongation rate is lower in the prior art.
In order to achieve the above object, the embodiment of the present invention provides the following technical solutions:
a high-extension ultrathin electronic copper foil is prepared by generating a green foil through direct current electroplating in electrolyte, and then carrying out surface treatment on the green foil in anti-oxidation liquid; wherein the electrolyte contains sulfuric acid, cupric ions, chloride ions and a proper amount of foil-forming additives; the raw foil additive comprises the following raw materials: sodium polydithio-dipropyl sulfonate, sodium N, N-dimethyl dithio carbonyl propane sulfonate, N- (3-sulfopropyl) -saccharin sodium salt, fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt, bone glue and polyethylene glycol.
Preferably, the oxidation preventing liquid contains 0.5-1.5g/L chromic anhydride, 1.0-5.0g/L sulfuric acid and a proper amount of glucose.
Further preferably, the additive amount of the green foil additive is 500-800ml/min.
Another object of the embodiment of the present invention is to provide a method for preparing a high-elongation ultrathin electronic copper foil, which includes the following steps: placing anode plate in electrolyte, performing DC electroplating under the action of DC to obtain green foil, and heating the green foil at 20-40deg.C and current density of 10-30A/m 2 And (3) placing the copper foil in an anti-oxidation liquid under the condition to perform surface treatment to obtain the high-elongation ultrathin electronic copper foil.
Further preferably, the preparation method of the high-elongation ultrathin electronic copper foil comprises the following steps:
(1) Electrolyte preparation
The electrolyte is prepared according to the dosage proportion of sulfuric acid, cupric ions, chloride ions and a proper amount of foil-forming additives.
(2) DC electroplating
The anode plate is placed in an electrolytic tank, electrolyte is placed in the electrolytic tank, copper ions are reduced on the surface of a titanium roller under the action of direct current, and an ultrathin electronic copper foil is deposited, namely, a green foil is generated through direct current electroplating.
(3) Oxidation preventing treatment
The raw foil is heated at 20-40deg.C and current density of 10-30A/m 2 And (3) placing the copper foil in an anti-oxidation liquid under the condition to perform surface treatment to obtain the high-elongation ultrathin electronic copper foil.
Another object of the embodiment of the present invention is to provide a high-elongation ultrathin electronic copper foil prepared by the above-mentioned preparation method of a high-elongation ultrathin electronic copper foil.
Another object of the embodiment of the present invention is to provide an application of the above-mentioned high-elongation ultrathin electronic copper foil in preparing lithium ion batteries.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
compared with the prior art, the invention is implementedThe high-elongation ultrathin electronic copper foil provided by the example is prepared by a raw foil additive process and a copper foil surface oxidation prevention process, and the tensile strength of the prepared high-elongation ultrathin electronic copper foil is greater than 30kgf/cm 2 The roughness is less than 2.0 mu m, the elongation is more than 15.0%, the copper foil has better mechanical property, good plasticity and elastic toughness, is not easy to deform, and solves the problem that the elongation is generally lower in the ultrathin electronic copper foil produced by the existing copper foil production enterprises. Moreover, the preparation method of the high-extension ultrathin electronic copper foil provided by the embodiment of the invention is simple, meanwhile, the method can continuously and stably produce, the system is easy to adjust, the foil manufacturing yield is high, and the market prospect is wide.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following description will briefly introduce the drawings that are needed in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention.
FIG. 1 is a 1000-fold SEM image of the smooth surface of a highly extended extra-thin electronic copper foil according to one embodiment of the present invention.
Fig. 2 is a 1000-fold SEM image of the matte surface of a high-elongation ultrathin electronic copper foil according to one embodiment of the invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clearly apparent, the technical schemes in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings. It will be apparent that the following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the present invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the spirit of the embodiments of the invention. These are all within the scope of embodiments of the present invention.
Specific implementations of the invention are described in detail below in connection with specific embodiments.
First, in recent years, as lithium batteries have been increased in capacity, thickness, density, and speed, the quality and performance of lithium copper foil have been improved. The lithium electric copper foil needs to have better mechanical property as a negative current collector, and the tensile strength and the elongation rate of the lithium electric copper foil need to meet certain requirements. The factors affecting the elongation mainly include the number of grain boundaries, the grain size, the slip system, the slip space orientation, and the anisotropy. In theory, then, extremely thin (. Ltoreq.6 μm) electronic copper foils, which are sought to have higher elongation properties, can be realized by the regulation of the above influencing factors.
In the prior art, an extremely thin (less than or equal to 6 mu m) copper foil is used in the current power lithium battery, and products with normal-temperature tensile strength of 300-350MPa mainly and elongation of more than or equal to 4% can be provided in the market generally. The elongation rate of the domestic extremely thin (less than or equal to 6 mu m) electronic copper foil is generally lower than 15%, which cannot meet the demands of customers on copper foil with higher elongation rate.
Therefore, in order to solve the above problems, the embodiment of the invention provides a high-extension ultrathin electronic copper foil which is suitable for preparing lithium ion batteries. The high-elongation ultrathin electronic copper foil is prepared by generating a green foil through direct current electroplating in electrolyte, and then carrying out surface treatment on the green foil in anti-oxidation liquid; wherein the electrolyte contains sulfuric acid, cupric ions, chloride ions and a proper amount of foil-forming additives; the raw foil additive comprises the following raw materials: sodium polydithio-dipropyl sulfonate, sodium N, N-dimethyl dithio carbonyl propane sulfonate, N- (3-sulfopropyl) -saccharin sodium salt, fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt (AESS), bone glue and polyethylene glycol. The prepared high-elongation ultrathin electronic copper foil has good elongation performance, wherein the elongation rate is more than 15%, and can meet the requirements of high-end clients.
In general, the raw foil additive contains an accelerator, a brightening agent, an inhibitor, a wetting agent, and the like as a surface active substance. The tensile strength of the prepared high-elongation ultrathin electronic copper foil is more than 30kgf/cm 2 The roughness is less than 2.0 mu m, the extensibility is more than 15.0 percent, and the alloy has better mechanical property, good plasticity, good elastic toughness and difficult deformation.
Further, the sodium polydithio-dipropyl sulfonate is typically a white or pale yellow powder, can be used in acidic copper plating brighteners to provide decorative and functional coatings, and can be used in combination with typical copper plating formulations such as nonionic surfactants, polyamines, and other mercapto compounds, without limitation.
As another preferred embodiment of the present invention, the bone cement is one of the most widely used animal based adhesive materials. Because of its beaded appearance, also known as beaded bone cement. The method is characterized in that: the adhesive has the advantages of good cohesiveness, high strength, less water, quick drying, good cohesiveness and shaping, low price and convenient use, is particularly suitable for cohering and pasting the fine-packaged book envelope, and can obtain good effect.
Preferably, the oxidation preventing liquid contains 0.5-1.5g/L chromic anhydride, 1.0-5.0g/L sulfuric acid and a proper amount of glucose.
Further, the oxidation preventing liquid contains 0.5-1.0g/L chromic anhydride, 1.0-2.0g/L sulfuric acid and 0.4g/L glucose.
Specifically, the chromic anhydride, namely chromium trioxide, is an inorganic compound, is dark red or dark purple crystalline powder, is dissolved in water, sulfuric acid, nitric acid, ethanol, diethyl ether, acetic acid and acetone, and is mainly used in electroplating industry, pharmaceutical industry, printing industry, tanning and fabric mordant.
Further, the average molecular weight of the polyethylene glycol is 1000-8000, namely, polyethylene glycol 1000, polyethylene glycol 2000, polyethylene glycol 3000, polyethylene glycol 4000, polyethylene glycol 6000, polyethylene glycol 8000 and other products can be specifically adopted.
Preferably, the polyethylene glycol has an average molecular weight of 8000, i.e., typically a relative molecular weight of 7500-8500.
As another preferable mode of the embodiment of the invention, the electrolyte contains sulfuric acid, cupric ions, chloride ions and a proper amount of foil-forming additive; specifically, the electrolyte contains 80-120g/L sulfuric acid, 80-100g/L cupric ion, 20-30ppm chloride ion and proper amount of foil producing additive.
As another preferable embodiment of the invention, the additive amount of the green foil additive in the electrolyte is 500-800ml/min.
As another preferable mode of the embodiment of the invention, the direct current plating to generate the green foil is at a temperature of 55-60 ℃ and a current density of 60-80A/dm 2 Is carried out under the condition of (2).
As another preferred embodiment of the present invention, the raw foil additive comprises the following raw materials in the following amounts:
as another preferred embodiment of the present invention, the raw foil additive comprises: sodium polydithio-dipropyl sulfonate, sodium N, N-dimethyl dithio carbonyl propane sulfonate, N- (3-sulfopropyl) -saccharin sodium salt, fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt (AESS), bone glue and polyethylene glycol. The ratio between the additives is 6.0:5.0:2.0:5.0:1.5:3.0. specifically, in order to further improve the elongation of extremely thin (less than or equal to 6 mu m) electronic copper foil, the elongation of the produced copper foil is more than 15% by providing a use scheme of a raw foil additive.
The embodiment of the invention also provides a preparation method of the high-elongation ultrathin electronic copper foil, which specifically comprises the following steps:
the copper foil produced by electroplating is processed at the temperature of 20-30 ℃ and the current density of 10-20A/m 2 And (3) placing the copper foil in an anti-oxidation liquid under the condition to perform surface treatment to obtain the high-elongation ultrathin electronic copper foil.
As another preferable mode of the embodiment of the invention, the oxidation preventing liquid contains 0.5-1.0g/L chromic anhydride, 1.0-2.0g/L sulfuric acid and 0.4g/L glucose, and the adding flow rate of the glucose is 100-300ml/min.
As another preferable mode of the embodiment of the invention, the preparation method of the high-elongation ultrathin electronic copper foil further comprises a regulating step, in particular to regulating electrolyte and antioxidant liquid. Specifically, for the electrolyte, the cupric ion, sulfuric acid concentration and chloride ion in the electrolyte are regulated to reach the expected indexes, the temperature of the electrolyte is regulated to a specified value, the raw foil additive is prepared and stirred uniformly according to a certain concentration, the raw foil additive is pre-added for 4-6 hours at a high-level tank according to a certain amount, so that the raw foil additive is fully dissolved and dispersed in the electrolyte, when the concentration of the raw foil additive in the electrolyte reaches the expected indexes, the electrolyte is electrified and started, and meanwhile, the adding amount of the raw foil additive is regulated to realize continuous guarantee of the using amount of the raw foil additive so as to maintain the consumption of the raw foil additive during electrolysis. And for the anti-oxidation liquid, adjusting the concentration and the temperature of hexavalent chromium ions and sulfuric acid in the anti-oxidation liquid to reach the expected indexes, pre-adding for 1-2 hours according to a certain amount, fully dissolving and dispersing the anti-oxidation liquid additive, and stopping adding when the concentration of the anti-oxidation liquid additive in the solution reaches the expected indexes. When the raw foil is started, an anti-oxidation power supply is started, the adding amount of the anti-oxidation liquid additive is adjusted, and the normal consumption of the anti-oxidation liquid additive is maintained continuously.
The embodiment of the invention also provides the high-extension ultrathin electronic copper foil prepared by the preparation method of the high-extension ultrathin electronic copper foil.
The embodiment of the invention also provides application of the high-extension ultrathin electronic copper foil in preparation of lithium ion batteries.
Specifically, the extremely thin (less than or equal to 6 mu m) electronic copper foil prepared by the using scheme of the additive has the thickness of 6 mu m and the elongation rate of more than 15 percent.
The technical effects of the high-elongation ultrathin electronic copper foil according to the embodiment of the invention are further described below by listing specific examples.
Example 1
A preparation method of a high-elongation ultrathin electronic copper foil comprises the steps of an electrolytic foil production process and a surface oxidation prevention process.
In this embodiment, the preparation method of the high-elongation ultrathin electronic copper foil specifically includes the following steps:
(1) Electrolytic foil production process: at a temperature of 55℃and a current density of 60A/dm 2 Electroplating on the surface of the cathode roller to form a green foil by using an electrolyte solution of 80g/L sulfuric acid, 80g/L cupric ions and 20ppm chloride ions, wherein the electrolyte solution comprises a green foil additive, and the green foil additive comprises sodium polydithio-dipropyl sulfonate, sodium N, N-dimethyl dithio carbonyl propane sulfonate and N- (3-sulfo)Propyl) -saccharin sodium salt, fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt (AESS), bone glue and polyethylene glycol, wherein the proportion of each additive is 5.0:1.8:3.0:4.0:6.0, additive flow rate 500ml/min.
(2) Surface oxidation prevention process: at a temperature of 20℃and a current density of 10A/dm 2 Performing surface electroplating treatment in 0.5g/L chromic anhydride and 1.0g/L sulfuric acid oxidation preventing liquid to obtain the high-elongation ultrathin electronic copper foil; the flow rate of the antioxidant liquid additive is 100ml/min.
(3) Adjusting the concentration of cupric ions, sulfuric acid and chloride ions in the electrolyte to reach the expected indexes, adjusting the temperature of the electrolyte to a specified value, preparing and stirring the additive uniformly according to a certain concentration, pre-adding the additive in a high-level tank for 4 hours according to a certain amount, fully dissolving and dispersing the additive in the electrolyte, powering on after the concentration of the additive in the electrolyte reaches the expected indexes, and simultaneously adjusting the adding amount of the additive to continuously add the additive so as to maintain the consumption during electrolysis.
(4) Adjusting the concentration and temperature of chromic anhydride and sulfuric acid in the anti-oxidation liquid to reach the expected index, preparing the additive which is uniformly stirred according to a certain concentration, pre-adding the additive for 1 hour according to a certain amount, fully dissolving and dispersing the additive, and stopping adding when the concentration of the additive in the solution reaches the expected index. When the raw foil is started, an anti-oxidation power supply is started, the addition amount of the additive is adjusted, and the additive is continuously consumed normally.
Example 2
The preparation method of the high-elongation ultrathin electronic copper foil comprises the specific steps of an electrolytic foil production process and a surface oxidation prevention process.
In this embodiment, the preparation method of the high-elongation ultrathin electronic copper foil specifically includes the following steps:
(1) Electrolytic foil production process: at a temperature of 58 ℃ and a current density of 70A/dm 2 Under the condition, the raw foil is electroplated on the surface of the cathode roller by using an electrolyte solution of 90g/L sulfuric acid, 90g/L cupric ions and 25ppm chloride ions. The remainder was the same as in example 1.
(2) Surface oxidation prevention process: the same as in example 1.
In this example, a Scanning Electron Microscope (SEM) examination was performed on a sample of the high-elongation ultrathin electronic copper foil produced, wherein a 1000-fold SEM picture of the smooth surface of the copper foil produced in example 2 is shown in fig. 1. The 1000-fold SEM image of the matte surface of the copper foil produced in example 2 is shown in fig. 2.
The growth of crystal grains and crystal faces, surface roughness, and texture of the copper foil are the main structural properties of the electrolytic copper foil. Wherein the influence of the texture on the copper foil is the greatest, and the texture is mainly reflected in the aspects of internal stress and mechanical property. Altering the texture of the copper foil is therefore critical to optimizing its textural properties. Factors influencing the elongation are mainly the number of grain boundaries-grain size, slip system-slip space orientation, anisotropy, etc. The ultrathin (less than or equal to 6 mu m) electronic copper foil with higher elongation performance can be realized by adjusting the formula proportion of the additive and influencing the crystal nucleation speed and the crystal size, and the electronic copper foil has the advantages of quick nucleation, quick growth of crystals and low elongation, and the contrary is the case.
As can be seen by combining fig. 1 and fig. 2, the high-extension ultrathin electronic copper foil prepared by the preparation method provided by the embodiment of the invention has good smooth surface roughness and overall flatness, high elongation (more than 15%), small fluctuation, high stability and high consistency, and can meet the requirements of high-end clients; the roughness Rz is small (< 2.0 μm) and the elongation is large (> 5.0%). Wherein, the additive system sodium polydithio-dipropyl sulfonate can improve the flatness and brightness of the copper foil; the bone glue can improve the normal-temperature tensile strength and the elongation of the copper foil; polyethylene glycol (preferably polyethylene glycol 8000) can refine grains and maintain leveling effect under high current; the N, N-dimethyl dithio carbonyl propane sodium sulfonate can enhance the elongation of the copper foil and improve the toughness of the copper foil; the N- (3-sulfopropyl) -saccharin sodium salt can refine crystallization, eliminate internal stress, prevent warpage and improve tensile strength and elongation. Fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt (AESS) is a surface wetting agent, can refine crystal grains, promote the lateral growth of copper foil, and avoid the problems of pinholes or penetration and the like of the ultrathin copper foil. Compared with the prior art, the elongation obtained by the production process is greatly improved compared with the prior ultrathin electronic copper foil.
Example 3
The preparation method of the high-elongation ultrathin electronic copper foil comprises the specific steps of an electrolytic foil production process and a surface oxidation prevention process.
In this embodiment, the preparation method of the high-elongation ultrathin electronic copper foil specifically includes the following steps:
(1) Electrolytic foil production process: at a temperature of 55℃and a current density of 60A/dm 2 Electroplating on the surface of a cathode roller by using an electrolyte of 80g/L sulfuric acid, 80g/L cupric ions and 30ppm chloride ions to generate a green foil, wherein the electrolyte comprises green foil additives, the green foil additives comprise sodium polydithio-dipropyl sulfonate, sodium N, N-dimethyl dithio carbonyl propane sulfonate, sodium N- (3-sulfopropyl) -saccharin, fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt (AESS), bone glue and polyethylene glycol, and the proportion of each additive is 2.0:1.0:1.0:4.0:6.0, additive flow rate 500ml/min.
(2) Surface oxidation prevention process: at a temperature of 20℃and a current density of 10A/dm 2 Performing surface electroplating treatment in 0.5g/L chromic anhydride and 1.0g/L sulfuric acid oxidation preventing liquid to obtain the high-elongation ultrathin electronic copper foil; the flow rate of the antioxidant liquid additive is 100ml/min.
(3) Adjusting the concentration of cupric ions, sulfuric acid and chloride ions in the electrolyte to reach the expected indexes, adjusting the temperature of the electrolyte to a specified value, preparing and stirring the additive uniformly according to a certain concentration, pre-adding the additive in a high-level tank for 4 hours according to a certain amount, fully dissolving and dispersing the additive in the electrolyte, powering on after the concentration of the additive in the electrolyte reaches the expected indexes, and simultaneously adjusting the adding amount of the additive to continuously add the additive so as to maintain the consumption during electrolysis.
(4) Adjusting the concentration and temperature of chromic anhydride and sulfuric acid in the anti-oxidation liquid to reach the expected index, preparing the additive which is uniformly stirred according to a certain concentration, pre-adding the additive for 1 hour according to a certain amount, fully dissolving and dispersing the additive, and stopping adding when the concentration of the additive in the solution reaches the expected index. When the raw foil is started, an anti-oxidation power supply is started, the addition amount of the additive is adjusted, and the additive is continuously consumed normally.
Example 4
The procedure of example 1 was repeated except that the electrolyte contained 120g/L sulfuric acid, 100g/L cupric ion and 30ppm chloride ion.
Example 5
The procedure of example 1 was repeated except that the electrolyte contained 110g/L sulfuric acid, 90g/L cupric ion and 25ppm chloride ion.
Example 6
In comparison with example 1, the raw materials of the foil additive were the same as in example 1 except that the raw materials included sodium polydithio-dipropyl sulfonate 60mg/L, N, sodium N-dimethyl dithio carbonyl propane sulfonate 40mg/L, N- (3-sulfopropyl) -saccharin sodium salt 40mg/L, fatty alcohol polyoxyethylene ether sulfonated succinic monoester disodium salt 40mg/L, bone glue 20mg/L, and polyethylene glycol 40 mg/L.
Example 7
In comparison with example 1, the raw materials of the foil additive were the same as in example 1 except that the raw materials included 120mg/L, N of sodium polydithio-dipropyl sulfonate, 120mg/L, N- (3-sulfopropyl) -saccharin sodium salt 160mg/L, fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt 160mg/L, bone glue 60mg/L, and polyethylene glycol 100mg/L.
Example 8
The procedure of example 1 was repeated except that the amount of the green foil additive in the electrolyte was 800ml/min as compared with example 1.
Example 9
The procedure of example 1 was repeated except that the antioxidant liquid contained 0.5g/L of chromic anhydride, 2.0g/L of sulfuric acid and 0.4g/L of glucose, and the flow rate of glucose was 300ml/min.
Example 10
The procedure of example 1 was repeated except that the antioxidant liquid contained 1.0g/L of chromic anhydride, 1.0g/L of sulfuric acid and 0.4g/L of glucose, and the flow rate of glucose was 100ml/min.
Performance detection
In order to verify the properties of the products prepared in the different examples and to determine the difference in merits between the different preparation methods, the raw foils prepared by electroplating in examples 1 to 3 were tested for properties such as tensile strength, elongation, surface roughness, etc., and the data obtained are shown in Table 1 below
Table 1 table of test results
As can be seen from the data in Table 1, the green foil prepared by the preparation method of the high-elongation ultrathin electronic copper foil provided by the embodiment of the invention has good elongation which can reach more than 15%.
Further, the oxidation resistance and dyne value of the high-elongation ultrathin electronic copper foil finally prepared by the preparation method in examples 1 to 3 were measured, and specific performance measurement results are shown in Table 2.
Table 2 table of performance test results
As can be seen from the data in table 2, the high-extension ultrathin electronic copper foil prepared by the preparation method of the high-extension ultrathin electronic copper foil provided by the embodiment of the invention has good oxidation resistance and good dyne value. The prepared ultrathin electronic copper foil has high elongation (more than 15%), small fluctuation, high stability and high consistency, and can meet the requirements of high-end clients; the roughness Rz is small (< 2.0 mu m), the extensibility is large (> 15.0%), and the appearance of the copper foil is uniform and good without flaws. The preparation method of the invention has the advantages of easy adjustment of the additive system, strong continuous production stability and high product yield.
According to the results, the beneficial effects of the embodiment of the invention are as follows, and the embodiment of the invention provides the high-extension ultrathin electronic copper foil, and the manufacturing method of the high-extension ultrathin electronic copper foil comprises a raw foil additive process and a copper foil surface oxidation prevention process. By utilizing additives having specific properties, the microstructure and grain orientation of the copper foil are altered, producing an extremely thin electronic copper foil with high elongation while maintaining a high level of tensile strength and roughness. In addition, the method can realize continuous and stable production, the system is easy to adjust, and the yield is high.
Moreover, the preparation method provided by the embodiment of the invention is simple and has wide market prospect. In the invention, sodium polydithio-dipropyl sulfonate, sodium N, N-dimethyl dithiocarbonyl propane sulfonate, sodium N- (3-sulfopropyl) -saccharin, fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt (AESS), bone glue, polyethylene glycol and the like are all products of the existing manufacturer. And is specifically selected according to needs, and is not described herein in detail.
The foregoing has outlined the more detailed description of the preferred embodiment of the invention in order that the basic principles, features and advantages of the invention may be described. However, it should be understood by those skilled in the art that the embodiments of the present invention are not limited to the foregoing embodiments, but rather the foregoing examples and descriptions are merely preferred examples of the present invention, and that various changes, modifications and variations may be made by those skilled in the art without departing from the spirit and scope of the invention, and equivalent changes may be made using the technical matters disclosed above; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the embodiments of the present invention.
Claims (10)
1. The high-extension ultrathin electronic copper foil is characterized in that the high-extension ultrathin electronic copper foil is prepared by generating a raw foil through direct current electroplating in electrolyte and then carrying out surface treatment on the raw foil in anti-oxidation liquid; wherein the electrolyte contains sulfuric acid, cupric ions, chloride ions and a proper amount of foil-forming additives; the raw foil additive comprises the following raw materials: sodium polydithio-dipropyl sulfonate, sodium N, N-dimethyl dithio carbonyl propane sulfonate, N- (3-sulfopropyl) -saccharin sodium salt, fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt, bone glue and polyethylene glycol.
2. The high extension ultrathin electronic copper foil according to claim 1, wherein the high extension ultrathin electronic copper foil has a tensile strength of more than 30kgf/cm 2 The roughness is less than 2.0 mu m, and the extensibility is more than 15.0 percent.
3. The highly extended ultrathin electronic copper foil according to claim 2, wherein the electrolyte contains 80-120g/L sulfuric acid, 80-100g/L cupric ion, 20-30ppm chloride ion and an appropriate amount of raw foil additive.
4. The high elongation ultrathin electronic copper foil according to claim 3, wherein the raw foil additive comprises the following raw materials in proportion:
60-120mg/L, N of sodium polydithio-dipropyl sulfonate, 40-120mg/L, N- (3-sulfopropyl) -saccharin sodium salt, 40-160mg/L of fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt, 20-60mg/L of bone glue and 40-100mg/L of polyethylene glycol.
5. The high elongation ultrathin electronic copper foil according to claim 4, wherein the raw foil additive comprises the following raw materials in parts by weight:
120mg/L, N of sodium polydithio-dipropyl sulfonate, 100mg/L, N of sodium N-dimethyl dithio carbonyl propane sulfonate, 40mg/L of sodium saccharin (3-sulfopropyl) -sodium salt, 100mg/L of fatty alcohol polyoxyethylene ether sulfonated succinic acid monoester disodium salt, 30mg/L of bone glue and 60mg/L of polyethylene glycol.
6. The highly extended ultrathin electronic copper foil according to claim 5, wherein the oxidation preventing liquid contains 0.5-1.5g/L chromic anhydride, 1.0-5.0g/L sulfuric acid and a proper amount of glucose.
7. A method for producing the high-elongation ultrathin electronic copper foil according to any one of claims 1 to 6, comprising the steps of:
placing anode plate in electrolyte, performing DC electroplating under the action of DC to obtain green foil, and heating the green foil at 20-40deg.C and current density of 10-30A/m 2 And (3) placing the copper foil in an anti-oxidation liquid under the condition to perform surface treatment to obtain the high-elongation ultrathin electronic copper foil.
8. The method for producing a highly extended ultrathin electronic copper foil according to claim 7, wherein in the method for producing a highly extended ultrathin electronic copper foil, the direct current plating is carried out at a temperature of 50 to 60℃and a current density of 50 to 100A/dm 2 Is carried out under the condition of (2).
9. A high-elongation ultrathin electronic copper foil produced by the production method of the high-elongation ultrathin electronic copper foil according to claim 7 or 8.
10. Use of the high extension ultrathin electronic copper foil according to claim 1 or 2 or 3 or 4 or 5 or 6 or 9 for preparing lithium ion batteries.
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